Physico-chemical characteristics of nano-organo bentonite prepared using different organo-modifiers

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A.M. Motawie

2014-09-01

Full Text Available Different types of nano-organo bentonite (NOB were prepared from the Egyptian Bentonite (EB. EB was characterized by energy dispersive X-ray EDX. It was purified from different impurities using a conventional method via the treatment with HCl and distilled water. The modification of the clay was carried out using different types of organo-modifiers namely; hexadecyl trimethyl ammonium bromide (HTAB, 3-aminopropyltriethoxysilane (Silane, octadecylamine (ODA, and dodecylamine (DDA. The cation exchange capacity (CEC was measured for pristine bentonite after and before modification. The NB was characterized by FTIR, XRD, TEM, and TGA techniques. The obtained results indicated that variation of the interlayer space gallery was effected by the type of the penetrator used.

Simultaneous selenate reduction and denitrification by a consortium of enriched mine site bacteria.

Science.gov (United States)

Subedi, Gaurav; Taylor, Jon; Hatam, Ido; Baldwin, Susan A

2017-09-01

Increasing selenium concentrations in aquatic environments downstream of mine sites is of great concern due to selenium's bioaccumulation propensity and teratogenic toxicity. Removal of selenium from mine influenced water is complicated by the presence of nitrate, which is also elevated in mine influenced water due to the use of explosives in mining. In many biological treatment processes, nitrate as a thermodynamically more preferable electron acceptor inhibits selenate reduction. Here we report on an enrichment of a bacterial assemblage from a mine impacted natural marsh sediment that was capable of simultaneous selenate reduction and denitrification. Selenate reduction followed first order kinetics with respect to the concentration of total dissolved selenium. The kinetic rate constant was independent of initial nitrate concentration over the range 3-143 mg L -1 -NO 3 - -N. The initial concentration of selenate inhibited selenate reduction kinetics over the range 1-24 mg-Se L -1 . Dominant taxa that grew in selenate only medium were classified in the genera Pseudomonas, Lysinibacillus and Thauera. When nitrate was introduced in addition to selenate, previously rare taxa that became dominant were relatives of Exiguobacterium, Tissierella and Clostridium. Open reading frames (ORFs) associated with dissimilatory denitrification were identified for Pseudomonas, Thauera and Clostridium. In addition, ORFs were found that were homologous with known selenate reductase subunits (SerA and SerB). These findings suggest that native mine site bacteria can be used for removing selenate and nitrate from mine wastewater. Crown Copyright © 2017. Published by Elsevier Ltd. All rights reserved.

Characteristics of CuInSe2 thin films grown by the selenization method

International Nuclear Information System (INIS)

Kim, Sang Deok; Kim, Hyeong Joon; Adurodija, Frederick Ojo; Yoon, Kyeong Hoon; Song, Jin Soo

1999-01-01

CuInSe 2 thin films were formed from a selenization of co-sputtered Cu-In alloy layers which consisted of only two phases, CuIn 2 and Cu 11 In 9 . A linear dependence of the Cu-In alloy film composition on the Cu/In sputtering power was found. The metallic layers were selenized in vacuum or at 1 atm. A small number of Cu-Se and In-Se compounds was observed during the early stage of selenization, and single-phase CuInSe 2 was more easily formed in vacuum than at atmospheric pressure. Therefore, CuInSe 2 films selenized in vacuum showed larger grain sizes, smoother surfaces, and denser microstructures than those selenized at 1 atm

Respiration of arsenate and selenate by hyperthermophilic archaea.

Science.gov (United States)

Huber, R; Sacher, M; Vollmann, A; Huber, H; Rose, D

2000-10-01

A novel, strictly anaerobic, hyperthermophilic, facultative organotrophic archaeon was isolated from a hot spring at Pisciarelli Solfatara, Naples, Italy. The rod-shaped cells grew chemolithoautotrophically with carbon dioxide as carbon source, hydrogen as electron donor and arsenate, thiosulfate or elemental sulfur as electron acceptor. H2S was formed from sulfur or thiosulfate, arsenite from arsenate. Organotrophically, the new isolate grew optimally in the presence of an inorganic electron acceptor like sulfur, selenate or arsenate. Cultures, grown on arsenate and thiosulfate or arsenate and L-cysteine, precipitated realgar (As2S2). During growth on selenate, elemental selenium was produced. The G+C content of the DNA was 58.3 mol%. Due to 16S rRNA gene sequence analysis combined with physiological and morphological criteria, the new isolate belongs to the Thermoproteales order. It represents a new species within the genus Pyrobaculum, the type species of which we name Pyrobaculum arsenaticum (type strain PZ6*, DSM 13514, ATCC 700994). Comparative studies with different Pyrobaculum-species showed, that Pyrobaculum aerophilum was also able to grow organotrophically under anaerobic culture conditions in the presence of arsenate, selenate and selenite. During growth on selenite, elemental selenium was formed as final product. In contrast to P. arsenaticum, P. aerophilum could use selenate or arsenate for lithoautotrophic growth with carbon dioxide and hydrogen.

Neutron activation analysis for study of distribution patterns of organo-halogen pollutants in apple

International Nuclear Information System (INIS)

Zhang Hong; Luo Jialing; Sun Huibin; Chai Zhifang; Chinese Academy of Sciences, Beijing

2007-01-01

The distribution characteristics of organo-halogens in apple and their sources were studied by neutron activation analysis combined with statistical analysis. The results indicated that concentrations of organo-halogens in apple were in the order of organo-chlorine >> organo-bromine > organo-iodine, and concentrations of the organo-chlorine in four parts of apple were in the order of seed >> peel >> endocarp ≥ pulp. Also, the organo-chlorine, -bromine and-iodine in apple were found to have different sources. The latter two were mainly from naturally synthetic products by plant itself, while the former was mainly from anthropogenic pollutants. (authors)

Uranyl fluoride luminescence in acidic aqueous solutions

International Nuclear Information System (INIS)

Beitz, J.V.; Williams, C.W.

1996-01-01

Luminescence emission spectra and decay rates are reported for uranyl species in acidic aqueous solutions containing HF or added NaF. The longest luminescence lifetime, 0.269 ± 0.006 ms, was observed from uranyl in 1 M HF + 1 M HClO 4 at 296 K and decreased with increasing temperature. Based on a luminescence dynamics model that assumes equilibrium among electronically excited uranyl fluoride species and free fluoride ion, this long lived uranyl luminescence in aqueous solution is attributed primarily to UO 2 F 2 . Studies on the effect of added LiNO 3 or Na 2 WO 4 ·2H 2 O showed relatively weak quenching of uranyl fluoride luminescence which suggests that high sensitivity determination of the UF 6 content of WF 6 gas should be feasible via uranyl luminescence analysis of hydrolyzed gas samples of impure WF 6

Characteristics of CuInSe sub 2 thin films grown by the selenization method

CERN Document Server

Kim, S D; Adurodija, F O; Yoon, K H; Song, J S

1999-01-01

CuInSe sub 2 thin films were formed from a selenization of co-sputtered Cu-In alloy layers which consisted of only two phases, CuIn sub 2 and Cu sub 1 sub 1 In sub 9. A linear dependence of the Cu-In alloy film composition on the Cu/In sputtering power was found. The metallic layers were selenized in vacuum or at 1 atm. A small number of Cu-Se and In-Se compounds was observed during the early stage of selenization, and single-phase CuInSe sub 2 was more easily formed in vacuum than at atmospheric pressure. Therefore, CuInSe sub 2 films selenized in vacuum showed larger grain sizes, smoother surfaces, and denser microstructures than those selenized at 1 atm.

Synthesis of 5-organo-, 9-organo-, and 9,11-diorgano-nido-7,8-dicarbaundecaborate salts by a cross-combination reaction

International Nuclear Information System (INIS)

Zakharkin, L.I.; Ol'shevskaya, V.A.; Petrovskij, P.V.

2000-01-01

It has been shown for the first time that salts of 5-iodine and 9,11-diiodine-nido-7,8-dicarbaundecaborates, containing iodine atoms near polyhedron pentagonal surface boron atoms, enter cross-combination reaction with magnesium organic compounds during catalysis by palladium complexes with formation of 5-organo-, 9-organo-, and 9,11-diorgano-nido-7,8-dicarbaundecaborate salts [ru

Preparation, characterization and thermal behaviour study of double selenates of lanthanides, yttrium and beryllium

International Nuclear Information System (INIS)

Ribeiro, C.A.

1988-01-01

The lanthanides (III) and yttrium (III) double selenates were studied using common analytical methods, atomic absorption, X-ray diffraction infra-red absorption, thermogravimetry and differential thermal analysis. These compounds were prepared from the mixture of lanthanides (III) and yttrium (III) selenates aqueous solution and basic beryllium selenates aqueous solution, obeying equimolar relation (1:1) to the cation

Uranyl tris-beta-diketonate complexes

International Nuclear Information System (INIS)

Sidorenko, G.V.; Adamov, V.M.; Shcherbakova, L.L.; Suglubov, D.N.

1986-01-01

Uranyl tris-pivaloyltrifluoroacetonates (M/IOTA/UO 2 L 3 ; M/IOTA/ = Na, K, Cs, 1/2Ba, NR 4 ; R = C 8 H 17 ) and tris-dipivaloylmethanate (M/IOTA/UO 2 L/IOTA/ 3 , M/IOTA/ = K) have been synthesized for the first time. The compounds were characterized by chemical analysis and IR, NMR, and mass spectra. NaUO 2 L 3 , KUO 2 L 3 , CsUO 2 L 3 and Ba(UO 2 ) 2 L 6 sublime in high vacuum with partial decomposition. Specifically, decomposition gives UL 4 , identified by mass spectrometry. All the tris-complexes except those with outer-sphere NR 4 cation are characterized by an asymmetric structure of the uranyl group, recorded by IR spectroscopy using isotopic substitution of 18 O in uranyl. NMR spectra of the tris-complexes indicate the equivalence of all beta-diketonate groups, i.e., a coordination number of six for uranyl

Removal of lead and phosphate ions from aqueous solutions by organo-smectite.

Science.gov (United States)

Bajda, Tomasz; Szala, Barbara; Solecka, Urszula

2015-01-01

Smectite has been modified using hexadecyltrimethyl ammonium bromide in an amount of double cationic exchange capacity. This alteration makes it possible to use organo-smectite as a sorbent to remove anionic forms. The experiment consisted of the interchangeable sorption of phosphate(V) and lead(II) by organo-smectite. Research was carried out with varying pH (2-5) and various concentrations (0.1-5 mmol/L). Organo-smectite with previously adsorbed lead ions removed more phosphate than the untreated organo-smectite. Experimental data show that lead is more likely to absorb on the organo-smectite than on the organo-smectite with previously adsorbed phosphate ions. It follows that the most effective use of the organo-smectite is through the sorption of first - Pb cations and then PO4 anions. With an increasing concentration of Pb(II) or P(V), the sorption efficiency increases. The maximum sorption efficiency of lead and phosphate ions is observed at pH 5. This enables the removal of harmful lead and phosphorus compounds from waste water and immobilizes them on the sorbent's surface. The alternating reactions of lead and phosphorus ions result in the crystallization of brompyromorphite Pb5(PO4)3Br.

Thin film solar cells by selenization sulfurization using diethyl selenium as a selenium precursor

Science.gov (United States)

Dhere, Neelkanth G.; Kadam, Ankur A.

2009-12-15

A method of forming a CIGSS absorber layer includes the steps of providing a metal precursor, and selenizing the metal precursor using diethyl selenium to form a selenized metal precursor layer (CIGSS absorber layer). A high efficiency solar cell includes a CIGSS absorber layer formed by a process including selenizing a metal precursor using diethyl selenium to form the CIGSS absorber layer.

Microfluidic-assisted fabrication of flexible and location traceable organo-motor.

Science.gov (United States)

Seo, Kyoung Duck; Kwak, Byung Kook; Sanchez, Samuel; Kim, Dong Sung

2015-04-01

In this paper, we fabricate a flexible and location traceable micromotor, called organo-motor, assisted by microfluidic devices and with high throughput. The organo-motors are composed of organic hydrogel material, poly (ethylene glycol) diacrylate (PEGDA), which can provide the flexibility of their structure. For spatial and temporal traceability of the organo-motors under magnetic resonance imaging (MRI), superparamagnetic iron oxide nanoparticles (SPION; Fe3O4) were incorporated into the PEGDA microhydrogels. Furthermore, a thin layer of platinum (Pt) was deposited onto one side of the SPION-PEGDA microhydrogels providing geometrical asymmetry and catalytic propulsion in aqueous fluids containing hydrogen peroxide solution, H2O2. Furthermore, the motion of the organo-motor was controlled by a small external magnet enabled by the presence of SPION in the motor architecture.

Entwicklung und Anwendung von Methoden zur Bestimmung von Selen-Spezies in human-biologischem Material

OpenAIRE

Jäger, Thomas

2014-01-01

Selen ist essentieller Bestandteil von mehr als 25 physiologisch wichtigen menschlichen Enzymen. Der tägliche Bedarf wird überwiegend in Form von organischen Selenverbindungen wie Selenmethionin oder Selenocystein aus der Nahrung aufgenommen. Weitere Expositionswege sind die Einnahme von Nahrungsergänzungsmitteln zur Selensupplementation sowie die inhalative oder dermale Aufnahme von in erster Linie anorganischen Selenverbindungen oder elementarem Selen an Arbeitsplätzen der Selen-verarbeiten...

Luminescence enhancement of uranyl ion by benzoic acid in acetonitrile

International Nuclear Information System (INIS)

Satendra Kumar; Maji, S.; Joseph, M.; Sankaran, K.

2014-01-01

Uranyl ion is known for its characteristic green luminescence and therefore luminescence spectroscopy is a suitable technique for characterizing different uranyl species. In aqueous medium, luminescence of uranyl ion is generally weak due to its quenching by water molecules and therefore in order to enhance the luminescence of uranyl ion in aqueous medium, luminescence enhancing reagents such as H 3 PO 4 , H 2 SO 4 , HCIO 4 have been widely used. The other method to enhance the uranyl luminescence is by ligand sensitized luminescence, a method well established for lanthanides. In this work, luminescence of uranyl ion is found to be enhanced by benzoic acid in acetonitrile medium. In aqueous medium benzoic acid does not enhance the uranyl luminescence although it forms 1:1 and 1:2 complexes with uranyl ion. Luminescence spectra of uranyl benzoate revealed that enhancement is due to sensitization of uranyl luminescence by benzoate ions. UV-Vis spectroscopy has been utilized to characterize the specie formed in the in acetonitrile medium. UV-Vis spectroscopy along with luminescence spectra revealed that the specie to be tribenzoate complex of uranyl (UO 2 (C 6 H 5 COO) 3 ) - having D 3 h symmetry. (author)

Sorption of uranyl ions on hydrous oxides

International Nuclear Information System (INIS)

Gupta, A.R.; Venkataramani, B.

1988-01-01

Sorption of uranyl ions on hydrous titanium oxide (HTiO), magnetite (MAG), and hydrous thorium oxide (HThO) has been studied as a function of pH. Hydrous oxides have been characterized by their pH-titration curves, intrinsic dissociation constants (pK ai * ) and point of zero charge (pH pzc ). The fraction of protonated surface hydroxyl groups as well as the surface pH (pH surf ) as a function of solution pH have been computed. The distribution of various hydrolyzed species of uranyl ions with solution pH have been compared with uranyl sorption isotherm on these oxides. Sorption edge in all the cases occurs when free hydroxyl groups are available on the surface and pH surf is sufficiently high to favor the formation of dimer-like species on the surface. A new model for the sorption process, called surface hydrolysis model, which explains these and other features of uranyl sorption on hydrous oxides has been proposed. The model visualizes the sorption process as linking of uranyl ions with two adjacent free surface hydroxyl groups without deprotonation (provided the surface pH is high for the hydrolysis of uranyl ions) and formation of dimer-like structures on the surface. The new model has been successfully applied to the present and other available data on uranyl ion sorption on hydrous oxides. (author)

Adsorption and desorption of cadmium by synthetic and natural organo-clay complexes

International Nuclear Information System (INIS)

Levy, R.; Francis, C.W.; Oak Ridge National Lab., Tenn.

1976-01-01

Tracer levels of 109 Cd were used to study the adsorption and desorption of Cd by synthetic and natural organo-clay complexes. Synthetic organo-clay complexes were made by adsorbing humic acid extracted from soil to various forms of 3 ) 2 showed that Cd was adsorbed more tenaciously to the sesquioxides than organo-clay fractions

Charge-density matching in organic-inorganic uranyl compounds

Energy Technology Data Exchange (ETDEWEB)

Krivovichev, S.V. [Saint Petersburg State Univ., Dept. of Crystallography, Faculty of Geology (Russian Federation); Krivovichev, S.V.; Tananaev, I.G.; Myasoedov, B.F. [Russian Academy of Sciences, A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Moscow (Russian Federation)

2007-10-15

Single crystals of [C{sub 10}H{sub 26}N{sub 2}][(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)](H{sub 2}SeO{sub 4}){sub 0.85}(H{sub 2}O){sub 2} (1), [C{sub 10}H{sub 26}N{sub 2}][(UO{sub 2})(SeO{sub 4}){sub 2}] (H{sub 2}SeO{sub 4}){sub 0.50}(H{sub 2}O) (2), and [C{sub 8}H{sub 20}N]{sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)] (H{sub 2}O) (3) were prepared by evaporation from aqueous solution of uranyl nitrate, selenic acid and the respective amines. The structures of the compounds have been solved by direct methods and structural models have been obtained. The structures of the compounds 1, 2, and 3 contain U and Se atoms in pentagonal bipyramidal and tetrahedral coordinations, respectively. The UO{sub 7} and SeO{sub 4} polyhedra polymerize by sharing common O atoms to form chains (compound 1) or sheets (compounds 2 and 3). In the structure of 1, the layers consisting of hydrogen-bonded [UO{sub 2}(SeO{sub 4}){sub 2}(H{sub 2}O)]{sup 2-} chains are separated by mixed organic-inorganic layers comprising from [NH{sub 3}(CH{sub 2}){sub 10}NH{sub 3}]{sup 2+} molecules, H{sub 2}O molecules, and disordered electroneutral (H{sub 2}SeO{sub 4}) groups. The structure of 2 has a similar architecture but a purely inorganic layer is represented by a fully connected [UO{sub 2}(SeO{sub 4}){sub 2}]{sup 2-} sheet. The structure of 3 does not contain disordered (H{sub 2}SeO{sub 4}) groups but is based upon alternating [UO{sub 2}(SeO{sub 4}){sub 2}(H{sub 2}O)]{sup 2-} sheets and 1.5-nm-thick organic blocks consisting of positively charged protonated octylamine molecules, [NH{sub 3}(CH{sub 2}){sub 7}CH{sub 3}]{sup +}. The structures may be considered as composed of anionic inorganic sheets (2D blocks) and cationic organic blocks self-organized according to competing hydrophilic-hydrophobic interactions. Analysis of the structures allows us to conclude that the charge-density matching principle is observed in uranyl compounds. In order to satisfy some basic peculiarities of uranyl (in

Quantification of uranyl in presence of citric acid

International Nuclear Information System (INIS)

Garcia G, N.; Barrera D, C.E.; Ordonez R, E.

2007-01-01

To determine the influence that has the organic matter of the soil on the uranyl sorption on some solids is necessary to have a detection technique and quantification of uranyl that it is reliable and sufficiently quick in the obtaining of results. For that in this work, it intends to carry out the uranyl quantification in presence of citric acid modifying the Fluorescence induced by UV-Vis radiation technique. Since the uranyl ion is very sensitive to the medium that contains it, (speciation, pH, ionic forces, etc.) it was necessary to develop an analysis technique that stands out the fluorescence of uranyl ion avoiding the out one that produce the organic acids. (Author)

Metal complex derivatives of hydrogen uranyl phosphate

International Nuclear Information System (INIS)

Grohol, D.; Blinn, E.L.

1994-01-01

Derivatives of hydrogen uranyl phosphate were prepared by incorporating transition metal complexes into the uranyl phosphate matrix. The transition metal complexes employed include bis(ethylenediamine)copper(II), bis(1,3-propanediamine)copper(II) chloride, (triethylenetetramine)copper(II), (1,4,8,11-tetraazacyclotetradecane)copper(II), (1,4,8,12-tetraazacyclopentadecane)copper(II), (1,4,8,11-tetraazacyclotetradecane)nickel(II) chloride, (triethylenetetramine)nickel(II) and others. The chemical analyses of these derivatives indicated that the incorporation of the transition metal complexes into the uranyl phosphate matrix via ion exchange was not stoichiometric. The extent of ion exchange is dependent on the size and structure of the transition metal complex. All complexes were characterized by X-ray powder diffractometry, electronic and infrared spectra, thermal analyses and chemical analysis. An attempt was made to correlate the degree of quenching of the luminescence of the uranyl ion to the spacing between the uranyl phosphate layers in the derivatives

Selenization of CIS and CIGS layers deposited by chemical spray pyrolysis

Energy Technology Data Exchange (ETDEWEB)

Babu, B. J.; Egaas, B.; Velumani, S.

2018-03-21

Cu(In1-xGax)Se2 (CIGS) thin films with x=0 (CIS) and x=0.3 (CIGS) were prepared on Mo-coated glass substrate by using chemical spray pyrolysis at a substrate temperature of 350 degrees C, followed by selenization treatment at 550 degrees C in selenium environment under N2 gas flow. X-ray diffraction patterns of as-deposited CIGS layers on Mo showed polycrystalline chalcopyrite phase with an intense (112) plane. Splitting of (204)/(220) and (116)/(312) planes for the film with x=0.3 reveals deviation of tetragonal nature. Field emission scanning electron microscopy cross-sectional images of selenized films showed clear re-crystallization of grains. During the selenization process of the CIGS absorber, a thin interface layer of MoSe2 is formed. Line mapping of Mo/CIGS layer showed more gallium segregation at the interface of back contact resulting in band gap grading. Chemical composition and mapping of the as-deposited and selenized samples were determined by energy dispersive analysis of X-rays. This work leads to fabrication of low cost and large scale Mo/CIGS/CdS/ZnO/ZnO:Al device structure.

Inhibition of synthesis of heparan sulfate by selenate: Possible dependence on sulfation for chain polymerization

International Nuclear Information System (INIS)

Dietrich, C.P.; Nader, H.B.; Buonassisi, V.; Colburn, P.

1988-01-01

Selenate, a sulfation inhibitor, blocks the synthesis of heparan sulfate and chondroitin sulfate by cultured endothelial cells. In contrast, selenate does not affect the production of hyaluronic acid, a nonsulfated glycosaminoglycan. No differences in molecular weight, [ 3 H]glucosamine/[ 35 S]sulfuric acid ratios, or disaccharide composition were observed when the heparan sulfate synthesized by selenate-treated cells was compared with that of control cells. The absence of undersulfated chains in preparations from cultures exposed to selenate supports the concept that, in the intact cell, the polymerization of heparan sulfate might be dependent on the sulfation of the saccharide units added to the growing glycosaminoglycan chain

Micro-SHINE Uranyl Sulfate Irradiations at the Linac

Energy Technology Data Exchange (ETDEWEB)

Youker, Amanda J. [Argonne National Lab. (ANL), Argonne, IL (United States); Kalensky, Michael [Argonne National Lab. (ANL), Argonne, IL (United States); Chemerisov, Sergey [Argonne National Lab. (ANL), Argonne, IL (United States); Schneider, John [Argonne National Lab. (ANL), Argonne, IL (United States); Byrnes, James [Argonne National Lab. (ANL), Argonne, IL (United States); Vandegrift, George F. [Argonne National Lab. (ANL), Argonne, IL (United States)

2016-08-01

Peroxide formation due to water radiolysis in a uranyl sulfate solution is a concern for the SHINE Medical Technologies process in which Mo-99 is generated from the fission of dissolved low enriched uranium. To investigate the effects of power density and fission on peroxide formation and uranyl-peroxide precipitation, uranyl sulfate solutions were irradiated using a 50-MeV electron linac as part of the micro-SHINE experimental setup. Results are given for uranyl sulfate solutions with both high and low enriched uranium irradiated at different linac powers.

Scaling Equation of State for Ferroelectric Triglycine Selenate at T ≈ Tc

NARCIS (Netherlands)

Iglesias, T.; Noheda, B.; Gallego, B.; Fernández del Castillo, J.R.; Lifante, G.; Gonzalo, J.A.

1994-01-01

Digital data of polarization vs. field on triglycine selenate at closely spaced temperature intervals (ΔT ≈ 0.015) in the vicinity of the quasi-tricritical point of triglycine selenate have been collected. These data fulfill very well the scaling equation of state ê± = ±p + (1/5)p5 (where ê- and ê+

Thermal decomposition of ammonium diuranate, uranyl nitrate hexahydrate and uranyl peroxide

International Nuclear Information System (INIS)

Yulianto, T.; Mutiara, E.

2011-01-01

The behaviors of three types of starting powder had been investigated during their thermal decomposition processes in nitrogen, air, and hydrogen. The powder types were the products of uranyl nitrate precipitation, i.e. ADU (ammonium diuranate), UNH (uranyl nitrate hexahydrate), and UPO (uranyl peroxide). The objective of the investigation was to find out the best atmosphere that would result in good quality powder in a thermal decomposition process with the lowest temperature and the shortest period of time in order to reduce the cost of UO 2 powder preparation. Before the thermal decomposition process was initiated, all powder types were characterized for their crystal structures. The investigation was conducted by TG-DTA instrument at temperature up to 800°C and the heating rate of 10°C/minute. The crystal structures were identified by X-Ray Diffractometer with Cu-Ka radiation. The specific surface area of the powder was also observed using BET method, especially for the powder that underwent the process in hydrogen heated up to 800°C. The Results showed that the process took place faster in hydrogen, and UNH required lower thermal decomposition temperature in relations with other types of powder. (author)

EXTRACTION OF URANYL NITRATE FROM AQUEOUS SOLUTIONS

Science.gov (United States)

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

1957-12-10

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

Thermal decomposition of double selenates of lanthanides (III), yttrium (III) and ammonium

International Nuclear Information System (INIS)

Crespi, M.S.

1989-01-01

Double selenates of lanthanides, yttrium and ammonium were prepared by treating mixtures of simple selenates with equimolar amounts and then dried in a vacuum desiccator containing anhydrous calcium chloride, protected from light. The compounds were studied using the conventional analytical methods such as infrared absorption spectra, X-ray diffraction, differential thermal analysis (DTA), and thermogravimetry (TG). (author)

Organo-axial volvulus of the small intestine: radiological case report and consideration for its mechanism.

Science.gov (United States)

Ishiguro, Toshitaka; Hiyama, Takashi; Nasu, Katsuhiro; Akashi, Yoshimasa; Minami, Manabu

2017-07-01

Gastrointestinal volvulus is mainly classified into two subtypes, mesentero-axial volvulus and organo-axial volvulus. The detailed imaging findings of organo-axial volvulus of the small intestine have never been reported as far as we know. In this article, we report a case of organo-axial volvulus of the small intestine, focusing on the computed tomography (CT) findings. An 80-year-old man was radiologically diagnosed as having organo-axial volvulus of the terminal ileum and it was confirmed by open surgery without adhesion or any other anatomical abnormalities. CT showed two specific findings, split-bowel sign and rotating-C sign, which we think reflect pathophysiologic features of organo-axial volvulus. We think the pathogenic mechanism of organo-axial volvulus can be explained by the convergence of the reversed-rotational twist following the formation of a twisted but non-obstructive circular loop, even if there is no adhesion. Radiologists should be aware that organo-axial volvulus can occur even in the small intestine, and in the case of small bowel obstruction with single transition point, the two pathophysiologic signs mentioned above must be looked for to diagnose the possibility of organo-axial volvulus.

Double selenates of rare earths and ammonium

International Nuclear Information System (INIS)

Iskhakova, L.D.; Kozlova, N.P.; Makarevich, L.G.

1991-01-01

Double selenates of rare earths with ammonium were prepared in result of crystallization. It is shown that NH 4 Ln(SeO 4 ) · nH 2 O crystalline hydrates are presented by penta-and trihydrates. Existance of two modifications was revealed for NH 4 Ln(SeO 4 ) · 5H 2 O: monoclinic form of NH 4 La(SeO 4 ) 2 · 5H 2 O, isostructural RbCe(SeO 4 ) 2 · 5H 2 O, and earlier unknown rhombic form of salts with Ln = Pr, Nd. Trihydrates with Ln = Sm-Yb belong to structural type of RbNd(SeO 4 ) 2 · 3H 2 O. Anhydrous salts NH 4 Ln(SeO 4 ) 2 are isostructural with monoclinic KNd(SO 4 ) 2 modification. Lattice parameters of binary selenates are presented

Splitting of the luminescent excited state of the uranyl ion

International Nuclear Information System (INIS)

Flint, C.D.; Sharma, P.; Tanner, P.A.

1982-01-01

The luminescence spectra of some uranyl compounds has been studied. It has been proposed that the splitting of the luminescent excited state of the uranyl ion is due to a descent in symmetry experienced by the uranyl ion when it is placed in a crystal field. In recent years there has been developed a highly successful model of the electronic structure of the uranyl ion. In this paper the authors use this model to interpret the luminescence spectra of a variety of uranyl compounds

On uranyl phosphites

International Nuclear Information System (INIS)

Avduevskaya, K.A.; Ragulina, N.B.; Rozanov, I.A.; Koval', E.M.

1978-01-01

The medium and single-substituted uranyl phosphites of the UO 2 HPO 3 x 3H 2 O and UO 2 (H 2 PO 3 ) 2 x3H 2 O composition were separated in crystal state for the first time. The medium phosphite is fully dehydrated above H 2 SO 4 , intermediate hydrates not being formed. Waterless phosphite decomposes at the temperature above 360 deg C into the mixture of uranium and uranyl phosphates, hydrogen being liberated. The thermal decomposition of single-substituted phosphite starts at the temperature above 150 deg C and is accompanied by the full reduction of uranium up to U(4). The product of calcination is identified as cubic UP 2 O 7

Uptake and Distribution of Added Selenite and Selenate by Barley and Red Clover as Influenced by Sulphur

DEFF Research Database (Denmark)

Nielsen, Gunnar Gissel

1973-01-01

The uptake of added Se from selenite and selenate by barley and red clover was investigated in a pot experiment. Much more of selenate than of selenite was taken up but the Se concentrations in the plants declined more with time when selenate was the source. Increasing sulphate addition to the soil...

In Situ Bioremediation of Perchlorate in Vadose Zone Soil Using Gaseous Electron Donors

Science.gov (United States)

2009-11-01

National Aeronautics and Space Administration ND Non-detect NDMA N-Nitrosodimethylamine No. Number NO3- Nitrate OD Outside diameter O&M...Nitrite xv • Selenate • Arsenate • Chromate and dichromate (i.e., hexavalent chromium) • Uranylate • Pertechnetate • N-Nitrosodimethylamine ( NDMA ...Arsenate • Chromate and dichromate (i.e., hexavalent chromium) • Uranylate • Pertechnetate • N-Nitrosodimethylamine ( NDMA ) • Trichloroethene (TCE

High-affinity uranyl-specific antibodies suitable for cellular imaging

International Nuclear Information System (INIS)

Reisser-Rubrecht, L.; Torne-Celer, C.; Renier, W.; Averseng, O.; Plantevin, S.; Quemeneur, E.; Bellanger, L.; Vidaud, C.

2008-01-01

Monoclonal antibodies (mAbs) have proved to be valuable models for the study of protein-metal interactions, and previous reports have described very specific antibodies to chelated metal ions, including uranyl. We raised specific mAbs against UO 2 2+ -DCP-BSA (DCP, 1, 10-phenanthroline-2,9-dicarboxylic acid) to generate new sets of antibodies that might cross-react with various complexed forms of uranyl in different environments for further application in the field of toxicology. Using counter-screening with UO 2 2+ -DCP-casein, we selected two highly specific mAbs against uranyl-DCP (K D = 10-100 pM): U04S and U08S. Competitive assays in the presence of different metal ions (UO 2 2+ , Fe 3+ , Zn 2+ , Cu 2+ , and Ca 2+ ) showed that uranyl in solution can act as a good competitor, suggesting some antibody ability to cross-react with chelating groups other than DCP in the UO 2 2+ equatorial coordination plane. Interestingly, one of the antibodies could be used for revealing uranyl cations in cell samples. Fluorescence activated cell sorting analyses after immuno-labeling revealed the interaction of uranyl with human kidney cells HK2. The intracellular accumulation of uranyl could be directly visualized by metal-immunostaining using fluorescent-labeled mAb. Our results suggest that U04S mAb epitopes mostly include the uranyl fraction and its para-topes can accommodate a wide variety of chelating groups. (authors)

A protein engineered to bind uranyl selectively and with femtomolar affinity

Science.gov (United States)

Zhou, Lu; Bosscher, Mike; Zhang, Changsheng; Özçubukçu, Salih; Zhang, Liang; Zhang, Wen; Li, Charles J.; Liu, Jianzhao; Jensen, Mark P.; Lai, Luhua; He, Chuan

2014-03-01

Uranyl (UO22+), the predominant aerobic form of uranium, is present in the ocean at a concentration of ~3.2 parts per 109 (13.7 nM) however, the successful enrichment of uranyl from this vast resource has been limited by the high concentrations of metal ions of similar size and charge, which makes it difficult to design a binding motif that is selective for uranyl. Here we report the design and rational development of a uranyl-binding protein using a computational screening process in the initial search for potential uranyl-binding sites. The engineered protein is thermally stable and offers very high affinity and selectivity for uranyl with a Kd of 7.4 femtomolar (fM) and >10,000-fold selectivity over other metal ions. We also demonstrated that the uranyl-binding protein can repeatedly sequester 30-60% of the uranyl in synthetic sea water. The chemical strategy employed here may be applied to engineer other selective metal-binding proteins for biotechnology and remediation applications.

Quasirelativistic pseudopotential study of species isoelectronic to uranyl and the equatorial coordination of uranyl

International Nuclear Information System (INIS)

Pyykkoe, P.; Li, J.; Runeberg, N.

1994-01-01

The calculated trends of geometries and vibrational frequencies of several uranyl isoelectronic species, like the known NUN and CUO, and the unknown CUN - , NUO + , and NUF 2+ , are reported. The NUN and CUO results support the matrix spectroscopic assignments. The simplest example of equatorial coordination to uranyl is the C 2d species UO 3 . Its calculated vibrational frequencies also support matrix spectroscopic ones. We earlier suggested that the large range of uranyl bond lengths in UO 6 6- -type systems could be interpreted in terms of a open-quotes frozen, soft e g vibrational modeclose quotes. Further studies on UF 6 , U(OH) 6 , [(OUO)(F eq ) n ] (n-2) -, [(OUO)(NO 3 ) 3 ] - , and [(OUO)(CO 3 ) 3 ] 4- show only small variation of R ax as function of R eq . Thus, the all-oxide case is a special one, where all ligands are capable of single and multiple bonding. 44 refs., 10 figs., 7 tabs

Determination of uranyl ion by potentiometric titration using an uranyl-selective electrode

International Nuclear Information System (INIS)

Nassory, N.S.

1990-01-01

A potentiometric titration of uranyl ion is described using an uranyl selective electrode based on a membrane containing a complex of UO 2 -bis[di-4-(1,1,3,3-tetramethylbutyl)phenyl phosphate] as an ion-exchanger and tritolyl phosphate as a solvent mediator. The titrations were carried out with various titrants: Sodium hydroxide, potassium fluoride and sodium salts of acetate, oxalate and citrate. The equivalence points were determined by Gran's method. Good results were obtained by using sodium oxalate as a titrant for the determination of uranium in several samples of ammonium diuranate. The results were quite comparable with those obtained by X-ray fluorescence spectrometry. (orig.)

Selen og vitamin E til svin

DEFF Research Database (Denmark)

Nielsen, H. E.; Danielsen, V.; Nielsen, Gunnar Gissel

1975-01-01

, kan der let opstå selenmangel. Vitamin E kan i nogen grad erstatte selen, men kun indenfor visse grænser. De senere års erfaringer har tydeligt vist, at der ofte opstår selenmangel, selvom der findes rigeligt E-vitamin i foderet. Resultaterne fra dette forsøg tyder på, at en nedsættelse af...

High-affinity uranyl-specific antibodies suitable for cellular imaging

Energy Technology Data Exchange (ETDEWEB)

Reisser-Rubrecht, L.; Torne-Celer, C.; Renier, W.; Averseng, O.; Plantevin, S.; Quemeneur, E.; Bellanger, L.; Vidaud, C. [CEA Valrho, DSV, IBEB, Serv Biochim et Toxicol Nucl, F-30207 Bagnols Sur Ceze (France)

2008-07-01

Monoclonal antibodies (mAbs) have proved to be valuable models for the study of protein-metal interactions, and previous reports have described very specific antibodies to chelated metal ions, including uranyl. We raised specific mAbs against UO{sub 2}{sup 2+}-DCP-BSA (DCP, 1, 10-phenanthroline-2,9-dicarboxylic acid) to generate new sets of antibodies that might cross-react with various complexed forms of uranyl in different environments for further application in the field of toxicology. Using counter-screening with UO{sub 2}{sup 2+}-DCP-casein, we selected two highly specific mAbs against uranyl-DCP (K{sub D} = 10-100 pM): U04S and U08S. Competitive assays in the presence of different metal ions (UO{sub 2}{sup 2+}, Fe{sup 3+}, Zn{sup 2+}, Cu{sup 2+}, and Ca{sup 2+}) showed that uranyl in solution can act as a good competitor, suggesting some antibody ability to cross-react with chelating groups other than DCP in the UO{sub 2}{sup 2+} equatorial coordination plane. Interestingly, one of the antibodies could be used for revealing uranyl cations in cell samples. Fluorescence activated cell sorting analyses after immuno-labeling revealed the interaction of uranyl with human kidney cells HK2. The intracellular accumulation of uranyl could be directly visualized by metal-immunostaining using fluorescent-labeled mAb. Our results suggest that U04S mAb epitopes mostly include the uranyl fraction and its para-topes can accommodate a wide variety of chelating groups. (authors)

The dehydration of uranyl nitrate hexahydrate

International Nuclear Information System (INIS)

Badalov, A.; Kamalov, D.D.; Khamidov, B.O.; Mirsaidov, I.U.; Eshbekov, N.R.

2010-01-01

Present article is devoted to study of dehydration process of uranyl nitrate hexahydrate. The dehydration process of uranyl nitrate hexahydrate was studied by means of tensimeter method with membrane zero-manometer. The research was carried out under equilibrium conditions. It was defined that in studied temperature ranges (300-450 K) the dehydration process of UO_2(NO_3)_2 has a three stage character.

Modeling selenate adsorption behavior on oxides, clay minerals, and soils using the triple layer model

Science.gov (United States)

Selenate adsorption behavior was investigated on amorphous aluminum oxide, amorphous iron oxide, goethite, clay minerals: kaolinites, montmorillonites, illite, and 18 soil samples from Hawaii, and the Southwestern and the Midwestern regions of the US as a function of solution pH. Selenate adsorpti...

Infrared Spectroscopy of Discrete Uranyl Anion Complexes

International Nuclear Information System (INIS)

Groenewold, G. S.; Gianotto, Anita K.; McIIwain, Michael E.; Van Stipdonk, Michael J.; Kullman, Michael; Moore, David T.; Polfer, Nick; Oomens, Jos; Infante, Ivan A.; Visscher, Lucas; Siboulet, Bertrand; De Jong, Wibe A.

2008-01-01

The Free-Electron Laser for Infrared Experiments (FELIX) w 1 as used to study the wavelength-resolved multiple photon photodissociation of discrete, gas phase uranyl (UO2 2 2+) complexes containing a single anionic ligand (A), with or without ligated solvent molecules (S). The uranyl antisymmetric and symmetric stretching frequencies were measured for complexes with general formula [UO2A(S)n]+, where A was either hydroxide, methoxide, or acetate; S was water, ammonia, acetone, or acetonitrile; and n = 0-3. The values for the antisymmetric stretching frequency for uranyl ligated with only an anion ([UO2A]+) were as low or lower than measurements for [UO2]2+ ligated with as many as five strong neutral donor ligands, and are comparable to solution phase values. This result was surprising because initial DFT calculations predicted values that were 30-40 cm-1 higher, consistent with intuition but not with the data. Modification of the basis sets and use of alternative functionals improved computational accuracy for the methoxide and acetate complexes, but calculated values for the hydroxide were greater than the measurement regardless of the computational method used. Attachment of a neutral donor ligand S to [UO2A]+ produced [UO2AS]+, which produced only very modest changes to the uranyl antisymmetric stretch frequency, and did not universally shift the frequency to lower values. DFT calculations for [UO2AS]+ were in accord with trends in the data, and showed that attachment of the solvent was accommodated by weakening of the U-anion bond as well as the uranyl. When uranyl frequencies were compared for [UO2AS]+ species having different solvent neutrals, values decreased with increasing neutral nucleophilicity

The interaction of uranyl ions with inorganic pyrophosphatase from baker's yeast

International Nuclear Information System (INIS)

Bienwald, B.; Heitmann, P.

1978-01-01

The interaction of uranyl ions with inorganic pyrophosphatase from baker's yeast was investigated by measurement of their effect on the protein fluorescence. Fluorescence titrations of the native enzyme with uranyl nitrate show that there is a specific binding of uranyl ions to the enzyme. It was deduced that each subunit of the enzyme binds one uranyl ion. The binding constant was estimated to be in the order of 10 7 M -1 . The enzyme which contains a small number of chemically modified carboxyl groups was not able to bind uranyl ions specifically. The modification of carboxyl groups was carried out by use of a water soluble carbodiimide and the nucleophilic reagent N-(2,4-dinitro-phenyl)-hexamethylenediamine. The substrate analogue calcium pyrophosphate displaced the uranyl ions from their binding sites at the enzyme From the results it is concluded that carboxyl groups of the active site are the ligands for the binding of uranyl ions. (author)

Thermal analysis studies of ammonium uranyl carbonate

International Nuclear Information System (INIS)

Cao Xinsheng; Ma Xuezhong; Wang Fapin; Liu Naixin; Ji Changhong

1988-01-01

The simultaneous thermogravimetry and differential thermal analysis of the ammonium uranyl carbonate powder were performed with heat balance in the following atmosphers: Air, Ar and Ar-8%H 2 . The thermogravimetry and differential thermal analysis curves of the ammonium uranyl carbonate powder obtained from different source were reported and discussed

Infrared spectra of volatile adduct of uranyl pivaloyltrifluoroacetonate with hexamethylphosphorotriamide

International Nuclear Information System (INIS)

Bukhmarina, V.N.; Dushin, R.B.; Sidorenko, G.V.; Suglobov, D.N.

1983-01-01

Adduct of uranyl pivaloyltrifluoroacetonate with hexamethylphosphortriamide (1), sublimated without decomposition and characterized by a high thermal stability, has been synthesized, as well as adducts of uranyl dipivaloylmethanate with hexamethylphosphortriamide (2) and dimethyl sulfoxide (3), sublimated with partial dissociation. IR spectra of crystalline adducts 1-3, their solutions in benzene; gaseous and matrix-isolated adduct 1 have been measured. It is shown that in gaseous phase 1 exists practically completely in non-dissociated form. It is detected that uranyl group in crystalline 1 and 2 and in matrix-isolated 1 in contrast to crystalline 3 and previously studied adducts of uranyl β-diketonates has an asymmetric structure. Strength constants of uranyl group in crystalline 1-3 and matrix-isolated 1 are determined

The chemical consequences of thermal neutron capture in alkali selenates

International Nuclear Information System (INIS)

Duplatre, G.; Vargas, J.I.

1977-01-01

The initial retention of the SeO 4 2- ion after thermal neutron capture has been studied in various matrices by chemical analysis. A comparison between the thermal behaviour of the chemically analyzed Sesup(IV) and the disappearance of the E.P.R. species SeO 3 - and SeO 4 3- showed that the retention fraction would include all species with oxidation state higher or equal to VI. The retentions observed in the different matrices show the existence of four families with respective retentions of: 2.6%[K 2 SeO 4 diluted in (NH 4 ) 2 SO 4 ], 9.2% [anhydrous and hydrated Li and Ca selenates; K 2 SeO 4 diluted in NaIO 3 ; Se + implanted in K 2 SeO 4 ; Triglycine selenate], 21.5% [K 2 SeO 4 diluted in KNO 3 , K 2 SO 4 , Na 2 WO 4 and Na 2 WO 4 .2H 2 O] and 32.0% [Na,K and Cs selenates]. Whereas chemical considerations may be invoked for the (NH 4 ) 2 SO 4 matrix, a mechanical model is proposed for the three other groups. (author)

Ligeti: Ricercare per organo / M. K.

Index Scriptorium Estoniae

M. K.

1991-01-01

Uuest heliplaadist "Ligeti: Ricercare per organo, Vivier, Les Communiantes, Cavana, Jodl; Scelsi: In nomine Lucis; Lennot: Livre d'Orgue-extrait; Richer: Orgue 88; Pärt: Pari intervallo, Pierre Bousseau (Orgel)" (AD:1990). Adda/TIS CD 581 240 (WD:59'45") DDD

Thermochemical investigations on uranyl phosphates and arsenates

International Nuclear Information System (INIS)

Barten, H.

1986-11-01

The results are described of a study of the thermochemical stability of anhydrous uranyl phosphates and arsenates. A number of aspects of chemical technological importance are indicated in detail. The synthesized anhydrous uranyl phosphates and arsenates were very hygroscopic, so that experiments on these compounds had to be carried out under moisture-free conditions. Further characterisation of these compounds are given, including a study of their thermal stabilities and phase relations. The uranyl phosphates reduced reversibly at temperatures of the order of 1100 to 1600 0 C. This makes it possible to express their relative stabilities quantitatively, in terms of the oxygen pressures of the reduction reactions. The thermal decomposition of uranyl arsenates did not occur by reduction, as for the phosphates, but by giving off arsenic oxide vapour. The results of measurements of enthalpies of solution led to the determination of the enthalpies of formation, heat capacity and the standard entropies of the uranyl arsenates. The thermochemical functions at high-temperatures could consequently be calculated. Attention is paid to the possible formation of uranium arsenates, whose uranium has a valency lower than six, hitherto not reported in literature. It was not possible to prepare arsenates of tetravalent uranium. However, three new compounds were observed, one of these, UAsO 5 , was studied in some detail. (Auth.)

40 CFR 721.5330 - Nickel salt of an organo compound containing nitrogen.

Science.gov (United States)

2010-07-01

... containing nitrogen. 721.5330 Section 721.5330 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5330 Nickel salt of an organo compound containing nitrogen. (a) Chemical... as nickel salt of an organo compound containing nitrogen (PMN P-92-686) is subject to reporting under...

Uranyl Oxalate Solubility

Energy Technology Data Exchange (ETDEWEB)

Leturcq, G.; Costenoble, S.; Grandjean, S. [CEA Marcoule DEN/DRCP/SCPS/LCA - BP17171 - 30207 Bagnols sur Ceze cedex (France)

2008-07-01

The solubility of uranyl oxalate was determined at ambient temperature by precipitation in oxalic-nitric solutions, using an initial uranyl concentration of 0.1 mol/L. Oxalic concentration varied from 0.075 to 0.3 mol/L while nitric concentration ranged between 0.75 and 3 mol/L. Dissolution tests, using complementary oxalic-nitric media, were carried out for 550 hours in order to study the kinetic to reach thermodynamic equilibrium. Similar solubility values were reached by dissolution and precipitation. Using the results, it was possible to draw the solubility surface versus oxalic and nitric concentrations and to determine both the apparent solubility constant of UO{sub 2}C{sub 2}O{sub 4}, 3H{sub 2}O (Ks) and the apparent formation constant of the first uranyl-oxalate complex UO{sub 2}C{sub 2}O{sub 4} (log {beta}1), for ionic strengths varying between 1 and 3 mol/L. Ks and log {beta}1 values were found to vary from 1.9 10{sup -8} to 9.2 10{sup -9} and from 5.95 to 6.06, respectively, when ionic strength varied from 1 to 3 mol/L. A second model may fit our data obtained at an ionic strength of 3 mol/L suggesting as reported by Moskvin et al. (1959) that no complexes are formed for [H{sup +}] at 3 M. The Ks value would then be 1.3 10{sup -8}. (authors)

Uranyl soaps - thermal, electronic and infrared spectral study

International Nuclear Information System (INIS)

Solanki, A.K.; Bhandari, A.M.

1981-01-01

The electronic and infrared spectra and TGA thermogram of uranyl soaps (laurate, mystrate, palmitate and stearate) have been studied. The environment about the UO 2+ 2 ion would comprise two 'short bite' bidentate carboxylate groups and oxygen atoms bridging from adjacent carboxylic molecules. The uranyl soaps have UO 2+ 2 vibronic absorption (approx. equal to 22730 cm -1 ) in the range found for eight coordinate uranyl complexes. The greater resistance to thermal degradation (approx. equal to 300 0 C) of these soaps and their stepwise thermal degradation infer strong metal-ligand interaction. (orig.) [de

Can uranyl complexes encapsulate to carbon nanotubes? A ...

Indian Academy of Sciences (India)

K SRINIVASU

We find that uranyl-aqua complex ([UO2(H2O)5]2+) binds stronger as compared to uranyl-hydroxo-complex .... until the maximum Hellmann–Feynman force on each atom ..... porters and near-infrared agents for selective cancer cell.

A novel selenization technique for fabrication of superconducting FeSex thin film

International Nuclear Information System (INIS)

Chai Qinglin; Tu Hailing; Hua Zhiqiang; Wang Lei; Qu Fei

2011-01-01

A novel selenization technique was applied to prepare superconducting FeSe x films with pre-set FeS films. The combination of reactive sputtering deposition with elemental diffusion technique would extend to prepare films of other iron-based superconductors. The results of transport measurement got close or greater than that of previous reports. T c,onset and T c,0 got to 10.2 K and 4 K respectively. We believe that increase of the content of Fe 7 Se 8 could not only reduce T c but also slow down the decline of resistivity. A combinative method with reactive sputtering deposition and selenization technique was applied to prepare superconducting FeSe x films on LaAlO 3 substrates successfully. The influence of selenizing temperature on film components was studied. FeSe 0.96 and FeSe films had similar and good performances in transport measurement but little difference in magnetic property. The critical onset temperature got to 11.2 K and T c,0 got to 4 K approximately. X-ray diffraction, energy dispersive spectroscopy and scanning electron microscopy were used to analyze the ratio of constituents and morphology of several selenized films. FeSe x film had a porous structure on surface and no well preferred orientation, which were confirmed to have little influence on superconducting properties.

SELENE - Self-Forming Extensible Lunar EVA Network, Phase I

Data.gov (United States)

National Aeronautics and Space Administration — The overall objective of this research effort (Phase I and Phase II) by Scientific Systems Company, Inc. and BBN Technologies is to develop the SELENE network --...

Uranyl sulfate irradiations at the Van de Graaff: A means to combat uranyl peroxide precipitation

Energy Technology Data Exchange (ETDEWEB)

Youker, Amanda J. [Argonne National Lab. (ANL), Argonne, IL (United States); Kalensky, Michael [Argonne National Lab. (ANL), Argonne, IL (United States); Quigley, Kevin J. [Argonne National Lab. (ANL), Argonne, IL (United States); Brossard, Thomas [Argonne National Lab. (ANL), Argonne, IL (United States); Chemerisov, Sergey D. [Argonne National Lab. (ANL), Argonne, IL (United States); Vandegrift, George F. [Argonne National Lab. (ANL), Argonne, IL (United States)

2017-05-01

As part of an effort to support SHINE Medical Technologies in developing a process to produce Mo-99 by neutron-induced fission, a series of irradiation experiments was performed with a 3 MeV Van de Graaff accelerator to generate high radiation doses in 0.5–2 mL uranyl sulfate solutions. The purpose was to determine what conditions result in uranyl peroxide precipitation and what can be done to prevent its formation. The effects of temperature, dose rate, uranium concentration, and the addition of known catalysts for the destruction of peroxide were determined.

Temperature and pH driven association in uranyl aqueous solutions

Directory of Open Access Journals (Sweden)

M. Druchok

2012-12-01

Full Text Available An association behavior of uranyl ions in aqueous solutions is explored. For this purpose a set of all-atom molecular dynamics simulations is performed. During the simulation, the fractions of uranyl ions involved in dimer and trimer formations were monitored. To accompany the fraction statistics one also collected distributions characterizing average times of the dimer and trimer associates. Two factors effecting the uranyl association were considered: temperature and pH. As one can expect, an increase of the temperature decreases an uranyl capability of forming the associates, thus lowering bound fractions/times and vice versa. The effect of pH was modeled by adding H+ or OH- ions to a "neutral" solution. The addition of hydroxide ions OH- favors the formation of the associates, thus increasing bound times and fractions. The extra H+ ions in a solution produce an opposite effect, thus lowering the uranyl association capability. We also made a structural analysis for all the observed associates to reveal the mutual orientation of the uranyl ions.

NMR as a tool for kinetic studies: application to the assessment of organo tin reactivity

Energy Technology Data Exchange (ETDEWEB)

Fouquet, E.; Roulet, T. [Bordeaux-1 Univ., 33 - Talence (France); Pianet, I. [Bordeaux-1 Univ., 33 -Talence (France) CNRS, Centre d`Etudes Structurales et d`Analyse des Molecules Organiques; Willem, R. [Brussels University (VUB), Brussels (Belgium)

1998-02-01

There is a growing interest for the research of an answer to the environmental problems related to the industrial use of tetra organo tins. An interesting alternative would be to develop the chemistry of mono organo tins because of their lower toxicity and of the easy removal of ``inorganic`` tin side products. In this work, halogen exchange rates are measured for various mono organo tins with NMR techniques (EXSY spectra and 1 D {sup 119} Sn NMR), and an exchange mechanism is proposed. A correlation between kinetic data and the reactivity of the mono organo tins is then exemplified with radical allylic transfer and palladium catalyzed coupling reactions. (authors) 14 refs.

IR spectra and structure of uranyl pivaloyltrifluoroacetylacetonate isolated in argon matrix

International Nuclear Information System (INIS)

Belyaeva, A.A.; Dushin, R.B.; Sidorenko, G.V.; Suglobov, D.N.

1985-01-01

When studying IR absorption spectra of a number of isotopomers of uranyl pivaloyl trifluoroacetonate (UPTFA), isolated in the matrix of argon and dissolved in benzene, and comparing them with the spectra of uranyl hexafluoroacetylacetonate (UHFA) vapours, it has been ascertained, that UPTFA vapours consist of monomers and dimers, and UPTFA solution in benzene - of dimers.It is shown, that the dimers have T-shaped structure, at that, the bond inside the dimer is realized by yl-atom of oxygen of an uranyl ion, included in the equatorial coordination sphere of another uranyl ion. Proofs of the dimer T-like structure distortion in gaseous or matrix-isolated state, as a result of which the difference of the angles between uranyl axes from 90 deg is observed, are given. In the framework of approximated model of isolated uranyl-ion the force constants for all the compounds investigated are calaculted

Specific capture of uranyl protein targets by metal affinity chromatography

International Nuclear Information System (INIS)

Basset, C.; Dedieu, A.; Guerin, P.; Quemeneur, E.; Meyer, D.; Vidaud, C.

2008-01-01

To improve general understanding of biochemical mechanisms in the field of uranium toxicology, the identification of protein targets needs to be intensified. Immobilized metal affinity chromatography (IMAC) has been widely developed as a powerful tool for capturing metal binding proteins from biological extracts. However uranyl cations (UO 2 2+ ) have particular physico-chemical characteristics which prevent them from being immobilized on classical metal chelating supports. We report here on the first development of an immobilized uranyl affinity chromatography method, based on the cation-exchange properties of amino-phosphonate groups for uranyl binding. The cation distribution coefficient and loading capacity on the support were determined. Then the stability of the uranyl-bonded phase under our chromatographic conditions was optimized to promote affinity mechanisms. The successful enrichment of uranyl binding proteins from human serum was then proven using proteomic and mass spectral analysis. (authors)

Electronic structure and properties of uranyl compounds. Problems of electron-donor conception

International Nuclear Information System (INIS)

Glebov, V.A.

1982-01-01

Comparison of the series of the ligand mutual substitution in the uranyl compounds with the ligand series of d-elements and with the uranyl ''covalent model'', is made. The data on ionization potentials of the ligand higher valent levels and on the structure of some uranyl nitrate compounds are considered. It is concluded that the mechanism of the ligand effect on the properties of uranyl grouping is more complex, than it is supposed in the traditional representations on the nature of electron-donor interactions in the uranyl compounds

Selenate as a novel ligand for keplerate chemistry. New {W72Mo60} keplerates with selenates inside the cavity.

Science.gov (United States)

Korenev, Vladimir S; Abramov, Pavel A; Vicent, Cristian; Zhdanov, Artem A; Tsygankova, Alphiya R; Sokolov, Maxim N; Fedin, Vladimir P

2015-05-21

The synthesis and characterization of three novel keplerate-type compounds containing the {W72Mo60} mixed-metal core are reported. Complexes (NH4)72[{W6O21(H2O)6}12{Mo2O4(SeO4)}30]·150H2O·6(NH4)2SeO4 (1a) and (NH4)25(NH2Me2)47[{W6O21(H2O)6}12{Mo2O4(SeO4)}30]·130H2O·3(NH4)2SeO4 (1b) were prepared by ligand substitution from the acetate anionic complex [{W6O21(H2O)5(CH3COO)0.5}12{Mo2O4(CH3COO)}30](48-) and selenate. The selenate anions in keplerate ions [{W6O21(H2O)6}12{Mo2O4(SeO4)}30](72-) are very labile and easily aquate with the formation of [{W6O21(H2O)6}12{Mo2O4}30(SeO4)20(H2O)20](52-), which was isolated as (NH4)20(NH2Me2)32[{W6O21(H2O)6}12{Mo2O4}30(SeO4)20(H2O)20]·150H2O (2) and structurally characterized. In the crystal structure of 2 selenate has several coordination modes, preferentially bonding to the {Mo2O4}(2+) units, and, additionally, to the {(W)W5} pentagonal blocks. The compounds have been characterized by elemental analysis, Raman, IR and (77)Se NMR spectroscopy, and by ESI mass spectrometry. Capillary electrophoresis was used for characterization of keplerates in solution for the first time.

Densities concentrations of aqueous of uranyl nitrate solutions

International Nuclear Information System (INIS)

Rodrigo Otero, A.; Rodriguez Hernandez, B.; Fernandez Rodriguez, L.

1966-01-01

The ratio density-concentration of aqueous uranyl nitrate solutions expressed as U 3 O 8 grams/liter, U grams/liter and hexahydrate uranyl nitrate weight percent at different temperatures, are established. Experimental values are graphically correlated and compared whit some published data. (Author) 2 refs

Photochemical reduction of uranyl ion by acetonitrile and propionitrile

International Nuclear Information System (INIS)

Brar, A.S.; Chander, R.; Sandhu, S.S.

1979-01-01

The photochemical reduction of uranyl ion by acetonitrile, propionitrile, benzonitrile, phenylacetonitrile, cyanoacetic acid and malononitrile in aqueous or aq. acetone medium using radiations >= 400 nm from a medium pressure mercury vapour lamp has been investigated. Except acetonitrile and propionitrile all other nitriles fail to bring about the reduction of uranyl ion. The reduction with aceto- and propionitriles has been found to obey pseudo-first order kinetics. The magnitude of rate of reduction with propionitrile is higher than that with acetonitrile. The pseudo-first order rate constants and quenching constant have been calculated from the kinetic data. It has been found that physical and chemical quenching compete with each other. The plot of reciprocal of quantum yield versus reciprocal (nitrile) is linear with a small intercept on the ordinate axis. Absorption spectra of uranyl ion in pure water, in the presence of acid and in the presence of acid+nitrile reveal that there is no ground state interaction between uranyl ion and the nitrile. A mechanism of photochemical reduction of uranyl ion based on α-hydrogen abstraction from the nitrile has been proposed. (auth.)

Raman spectral titration method: an informative technique for studying the complexation of uranyl with uranyl(vi)-DPA/oxalate systems as examples.

Science.gov (United States)

Liu, Qian; Zhang, Qianci; Yang, Suliang; Zhu, Haiqiao; Liu, Quanwei; Tian, Guoxin

2017-10-10

The Raman band at about 870 cm -1 originating from the symmetric stretch vibration (ν 1 ) of uranyl, UO 2 2+ , has proven to be very informative for investigating the complexation of uranyl using perchlorate or nitrate of known concentration as internal standards. The concentration of uranyl can be conveniently calculated by using the ratio of the directly read band intensities of uranyl and the added reference, ClO 4 - , with a factor of 1.72. While with NO 3 - of concentration lower than 1.8 M as the reference, a factor of 0.85 should be used. Furthermore, with added internal standards, the linear relationship between the Raman intensity and the concentration of the corresponding species is illustrated by the spectral titration of U(vi) with a very strong ligand, dipicolinic acid (DPA); and the application of a spectral titration method with Raman spectroscopy in studying the complexation of uranyl is demonstrated by the titration of U(vi) with oxalate. The stepwise changes in the Raman shift of 18, 17, and 6 cm -1 , corresponding to the three oxalate anions successively bonding to UO 2 2+ , imply that the coordination modes are different. In the 1 : 1 and 1 : 2 ratios of metal to ligand complexes, the oxalate anions bond to the uranyl ion in side-on bidentate mode, but in the 1 : 3 complex the third oxalate bonds in head-on mode, which is much weaker than the first two.

Optimization of selenizing conditions for Seleno-Lentinan and its characteristics.

Science.gov (United States)

Ren, Guangming; Li, Koukou; Hu, Yang; Yu, Min; Qu, Juanjuan; Xu, Xiuhong

2015-11-01

Lentinan was successfully modified with nitric acid-sodium selenite method based on L9(3(4)) orthogonal experiments. The optimum selenizing conditions were obtained according to selenium conversion rate as follows: Lentinan of 1.0g, pH of 4.5, temperature of 70°C and sodium selenite of 1.50g. The antioxidant activity assays in vitro (DPPH, reducing power, superoxide radicals and hydroxyl radicals) proved that Lentinan had stronger antioxidant activity after selenizing. The elevations of serum alanine aminotransferase and aspartate aminotransferase, as well as the abnormal hepatic architecture, verified that oral administration of Seleno-Lentinan (SL2-1) markedly alleviated oxidative damage in the liver of mice induced by D-gal. In addition, SL2-1 significantly increased total antioxidant capacity, activities and protein expressions of catalase and glutathione peroxidase and lowered malondialdehyde levels in serum and liver. Fourier transform infrared spectroscopy analysis indicated that selenium of SL2-1 was mostly existed as the formations of OSeO, SeO and SeOC. Scanning electron microscope coupled with energy dispersive X-ray spectroscopy analysis revealed that the surface structure and elemental components of Lentinan significantly changed after selenizing. The results are instructive for the development of organic selenium-supplement resource. Copyright © 2015 Elsevier B.V. All rights reserved.

Preliminary observations on the effects of selenate on the development of the embryonic skate, Raja eglanteria

Science.gov (United States)

Conrad, G. W.; Luer, C. A.; Paulsen, A. Q.; Funderburgh, J. L.; Spooner, B. S. (Principal Investigator)

1993-01-01

Morphogenesis of the clearnose skate, Raja eglanteria, was not significantly inhibited as a result of 7 days of exposure to 1-2 mM selenate in the sea water during Days 59-69 of embryonic development (hatching would normally have occurred at 82 +/- 4 days of incubation). Although corneal transparency appeared normal in the eye, preliminary measurements of the thickness of Bowman's layer of the cornea suggested that it was significantly thinner in the corneas of embryos exposed to 1-2 mM selenate. Selenate is an ion reported to inhibit sulfation of glycosaminoglycans in connective tissue.

Synthesis and characterization of heterometallic uranyl pyridinedicarboxylate compounds

Science.gov (United States)

Jayasinghe, Ashini S.; Payne, Maurice K.; Forbes, Tori Z.

2017-10-01

The incorporation of transition metals into hybrid uranyl materials can result in more diverse structural topologies and variations in physical and chemical properties. To explore the impact of transition metals on the uranyl cation, five uranium containing bimetallic chain compounds, [(UO2)M(PDC)2(H2O)4]·4(H2O) (PDC = 2,6 pyridinedicarboxylate; M = Ni2+, Co2+, Fe2+, Zn2+, and Cu2+) were synthesized by evaporation of aqueous solutions at room temperature. The uranyl cation is complex by two PDC ligands and the transition metal cations bond to the complex to form a one-dimensional chain topology. The presence of the transition metal leads to the presence of a stronger uranyl oxo bonds as shown by the single-crystal X-ray diffraction data and the Raman spectra. Solid state diffuse reflectance UV/Visible spectra confirmed the presence of the transition metals in the structure by the broad bands that appeared at relevant wavelengths.

Potentiometric titration of selenic and telluric acids with titanium(III) chloride in nonaqueous solvents

International Nuclear Information System (INIS)

Yoshimura, Chozo; Miyamoto, Kiyoshige

1985-01-01

Selenic and Telluric acids were titrated potentiometrically with titanium(III) chloride solution by using Pt-Cu · Hg bimetallic electrodes in nonaqueous solvents such as N, N-dimethyl-formamide (DMF), dimethyl sulfoxide (DMSO), isopropyl alcohol (IPA) and the mixtures of these solvents. It was found that selenic and telluric acids were titrated directly at room temperature in DMF solution without hydrochloric acid. The molar ratios of selenic and telluric acids to titanium(III) chloride was 1 : 6. However, the corresponding reactions to SeO 4 2- → SeO 3 2- or TeO 4 2- → TeO 3 2- were not confirmed in the titration curve in DMF. In the titration of selenic acid in mixed solvents of DMF and IPA in 1 : 1 or 1 : 2 ratio, two steps were observed. The first and the second steps were appeared on the titration curve at molar ratios of 1 : 2 and 1 : 6, respectively. It was interpreted that the first step corresponded to the intermediate reaction of SeO 4 2- → SeO 3 2- . Mixed solution of selenic and telluric acids were determined by the proposed method. Three steps were observed on the titration curve. It was interpreted that the first, second and third steps corresponded to the reaction of SeO 4 2- → SeO 3 2- , SeO 3 2- → Se(0), and TeO 4 2- → Te(0), respectively. Less than 5 % of water gave no influence on the titration. (author)

Multi-scale modelling of uranyl chloride solutions

Energy Technology Data Exchange (ETDEWEB)

Nguyen, Thanh-Nghi; Duvail, Magali, E-mail: magali.duvail@icsm.fr; Villard, Arnaud; Dufrêche, Jean-François, E-mail: jean-francois.dufreche@univ-montp2.fr [Institut de Chimie Séparative de Marcoule (ICSM), UMR 5257, CEA-CNRS-Université Montpellier 2-ENSCM, Site de Marcoule, Bâtiment 426, BP 17171, F-30207 Bagnols-sur-Cèze Cedex (France); Molina, John Jairo [Fukui Institute for Fundamental Chemistry, Kyoto University, Takano-Nishihiraki-cho 34-4, Sakyo-ku, Kyoto 606-8103 (Japan); Guilbaud, Philippe [CEA/DEN/DRCP/SMCS/LILA, Marcoule, F-30207 Bagnols-sur-Cèze Cedex (France)

2015-01-14

Classical molecular dynamics simulations with explicit polarization have been successfully used to determine the structural and thermodynamic properties of binary aqueous solutions of uranyl chloride (UO{sub 2}Cl{sub 2}). Concentrated aqueous solutions of uranyl chloride have been studied to determine the hydration properties and the ion-ion interactions. The bond distances and the coordination number of the hydrated uranyl are in good agreement with available experimental data. Two stable positions of chloride in the second hydration shell of uranyl have been identified. The UO{sub 2}{sup 2+}-Cl{sup −} association constants have also been calculated using a multi-scale approach. First, the ion-ion potential averaged over the solvent configurations at infinite dilution (McMillan-Mayer potential) was calculated to establish the dissociation/association processes of UO{sub 2}{sup 2+}-Cl{sup −} ion pairs in aqueous solution. Then, the association constant was calculated from this potential. The value we obtained for the association constant is in good agreement with the experimental result (K{sub UO{sub 2Cl{sup +}}} = 1.48 l mol{sup −1}), but the resulting activity coefficient appears to be too low at molar concentration.

Uranyl Sulfate Nanotubules Templated by N-phenylglycine

Directory of Open Access Journals (Sweden)

Oleg I. Siidra

2018-04-01

Full Text Available The synthesis, structure, and infrared spectroscopy properties of the new organically templated uranyl sulfate Na(phgH+7[(UO26(SO410](H2O3.5 (1, obtained at room temperature by evaporation from aqueous solution, are reported. Its structure contains unique uranyl sulfate [(UO26(SO410]8− nanotubules templated by protonated N-phenylglycine (C6H5NH2CH2COOH+. Their internal diameter is 1.4 nm. Each of the nanotubules is built from uranyl sulfate rings sharing common SO4 tetrahedra. The template plays an important role in the formation of the complex structure of 1. The aromatic rings are stacked parallel to each other due to the effect of π–π interaction with their side chains extending into the gaps between the nanotubules.

Photochemical reduction of uranyl ion with triphenylphosphine

International Nuclear Information System (INIS)

Brar, A.S.; Sidhu, M.S.; Sandhu, S.S.

1981-01-01

Photochemical reduction of uranyl ion with triphenylphosphine has been studied in acetone-water medium in the presence of sulphuric acid at 346nm, 400nm and 434nm wavelengths. The photochemical reduction is of second order and increases with increase in hydrogen ion concentration. Absorption spectra of uranyl ion in acidic medium and uranyl ion with triphenylphosphine do not show any ground state complex formation. The value of quantum yield increases with the wavelength of the radiation increase from 346 to 434nm. Plots of reciprocal of quantum yield for the formation of U(IV) versus reciprocal [triphenylphosphine] are linear. Products characterized by UV and visible, IR and TLC show the formation of U(IV) and triphenylphosphine oxide. On the basis of above observations mechanism of the photochemical reduction has been proposed. (author)

Benchmarking uranyl peroxide capsule chemistry in organic media

Energy Technology Data Exchange (ETDEWEB)

Neal, Harrison A.; Nyman, May [Department of Chemistry, Oregon State University, Corvallis, OR (United States); Szymanowski, Jennifer; Fein, Jeremy B.; Burns, Peter C. [Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, IN (United States)

2017-01-03

Uranyl peroxide capsules are a recent addition to polyoxometalate (POM) chemistry. Ten years of development has ensued only in water, while transition metal POMs are commonly exploited in aqueous and organic media, controlled by counterions or ligation to render the clusters hydrophilic or hydrophobic. Here, new uranyl POM behavior is recognized in organic media, including (1) stabilization and immobilization of encapsulated hydrophilic countercations, identified by Li nuclear magnetic resonance (NMR) spectroscopy, (2) formation of new cluster species upon phase transfer, (3) extraction of uranyl clusters from different starting materials including simulated spent nuclear fuel, (4) selective phase transfer of one cluster type from a mixture, and (5) phase transfer of clusters from both acidic and alkaline media. The capsule morphology of the uranyl POMs renders accurate characterization by X-ray scattering, including the distinction of geometrically similar clusters. Compositional analysis of the aqueous phase post-extraction provided a quantitative determination of the ion exchange process that enables transfer of the clusters into the organic phase. Preferential partitioning of uranyl POMs into organic media presents new frontiers in metal ion behavior and chemical reactions in the confined space of the cluster capsules in hydrophobic media, as well as the reactivity of clusters at the organic/aqueous interface. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Benchmarking uranyl peroxide capsule chemistry in organic media

International Nuclear Information System (INIS)

Neal, Harrison A.; Nyman, May; Szymanowski, Jennifer; Fein, Jeremy B.; Burns, Peter C.

2017-01-01

Uranyl peroxide capsules are a recent addition to polyoxometalate (POM) chemistry. Ten years of development has ensued only in water, while transition metal POMs are commonly exploited in aqueous and organic media, controlled by counterions or ligation to render the clusters hydrophilic or hydrophobic. Here, new uranyl POM behavior is recognized in organic media, including (1) stabilization and immobilization of encapsulated hydrophilic countercations, identified by Li nuclear magnetic resonance (NMR) spectroscopy, (2) formation of new cluster species upon phase transfer, (3) extraction of uranyl clusters from different starting materials including simulated spent nuclear fuel, (4) selective phase transfer of one cluster type from a mixture, and (5) phase transfer of clusters from both acidic and alkaline media. The capsule morphology of the uranyl POMs renders accurate characterization by X-ray scattering, including the distinction of geometrically similar clusters. Compositional analysis of the aqueous phase post-extraction provided a quantitative determination of the ion exchange process that enables transfer of the clusters into the organic phase. Preferential partitioning of uranyl POMs into organic media presents new frontiers in metal ion behavior and chemical reactions in the confined space of the cluster capsules in hydrophobic media, as well as the reactivity of clusters at the organic/aqueous interface. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Aggregation-induced emission active tetraphenylethene-based sensor for uranyl ion detection

Energy Technology Data Exchange (ETDEWEB)

Wen, Jun; Huang, Zeng; Hu, Sheng [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang, 621900, Sichuan Province (China); Li, Shuo, E-mail: lishuo@cqut.edu.cn [School of Chemical Engineering, Chongqing University of Technology, Chongqing 400054 (China); Li, Weiyi, E-mail: weiyili@mail.xhu.edu.cn [School of Science, Xihua University, Chengdu, Sichuan, 610065 (China); Wang, Xiaolin, E-mail: xlwang@caep.cn [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang, 621900, Sichuan Province (China)

2016-11-15

Highlights: • A novel AIE fluorescent sensor for the detection of uranyl has been developed. • TPE-T is capable of visually distinguish UO{sub 2}{sup 2+} among many metals owing to the AIE phenomenon. • TPE-T showed a wide effective pH range, high selectivity and good anti-interference qualities. • TPE-T showed good accuracy in the determination of uranyl in river water. - Abstract: A novel tetraphenylethene-based fluorescent sensor, TPE-T, was developed for the detection of uranyl ions. The selective binding of TPE-T to uranyl ions resulted in a detectable signal owing to the quenching of its aggregation-induced emission. The developed sensor could be used to visually distinguish UO{sub 2}{sup 2+} from lanthanides, transition metals, and alkali metals under UV light; the presence of other metal ions did not interfere with the detection of uranyl ions. In addition, TPE-T was successfully used for the detection of uranyl ions in river water, illustrating its potential applications in environmental systems.

Evaluation of the stability of uranyl peroxo-carbonato complex ions in carbonate media at different temperatures

International Nuclear Information System (INIS)

Kim, Kwang-Wook; Lee, Keun-Young; Chung, Dong-Yong; Lee, Eil-Hee; Moon, Jei-Kwon; Shin, Dong-Woo

2012-01-01

Highlights: ► The stability of peroxide in uranyl peroxo carbonato complex solutions with different temperatures was characterized. ► The decomposition rate of uranyl peroxo carbonato complex ion to uranyl tris-carbonato complex ion was observed to increase with temperature ► The decomposition kinetics of uranyl peroxo carbonato complex ions was evaluated by absorption and Raman spectroscopies. ► A precipitate of uranyl peroxo carbonato complex solution was evaluated with XRD. - Abstract: This work studied the stability of peroxide in uranyl peroxo carbonato complex ions in a carbonate solution with hydrogen peroxide using absorption and Raman spectroscopies, and evaluated the temperature dependence of the decomposition characteristics of uranyl peroxo carbonato complex ions in the solution. The uranyl peroxo carbonato complex ions self-decomposed more rapidly into uranyl tris-carbonato complex ions in higher temperature carbonate solutions. The concentration of peroxide in the solution without free hydrogen peroxide represents the concentration of uranyl peroxo carbonato complex ions in a mixture of uranyl peroxo carbonato complex and uranyl tris-carbonato complex ions. The self-decomposition of the uranyl peroxo carbonato complex ions was a first order reaction, and its activation energy was evaluated to be 7.144 × 10 3 J mol −1 . The precipitation of sodium uranium oxide hydroxide occurred when the amount of uranyl tris-carbonato complex ions generated from the decomposition of the uranyl peroxo carbonato complex ions exceeded the solubility of uranyl tris-carbonato ions in the solution at the solution temperature.

Organo-Selenium Coatings Inhibit Gram-Negative and Gram-Positive Bacterial Attachment to Ophthalmic Scleral Buckle Material.

Science.gov (United States)

Tran, Phat; Arnett, Avery; Jarvis, Courtney; Mosley, Thomas; Tran, Khien; Hanes, Rob; Webster, Dan; Mitchell, Kelly; Dominguez, Leo; Hamood, Abdul; Reid, Ted W

2017-09-01

Biofilm formation is a problem for solid and sponge-type scleral buckles. This can lead to complications that require removal of the buckle, and result in vision loss due to related ocular morbidity, primarily infection, or recurrent retinal detachment. We investigate the ability of a covalent organo-selenium coating to inhibit biofilm formation on a scleral buckle. Sponge and solid Labtican brand scleral buckles were coated with organo-selenium coupled to a silyation reagent. Staphylococcus aureus biofilm formation was monitored by a standard colony-forming unit assay and the confocal laser scanning microscopy, while Pseudomonas aeruginosa biofilm formation was examined by scanning electron microscopy. Stability studies were done, by soaking in phosphate buffer saline (PBS) at room temperature for 2 months. Toxicity against human corneal epithelial cell was examined by growing the cells in the presence of organo-selenium-coated scleral buckles. The organo-selenium coating inhibited biofilm formation by gram-negative and gram-positive bacteria. The buckle coatings also were shown to be fully active after soaking in PBS for 2 months. The organo-selenium coatings had no effect on the viability of human corneal epithelial cells. Organo-selenium can be used to covalently coat a scleral buckle, which is stable and inhibits biofilm formation for gram-negative and gram-positive bacteria. The organo-selenium buckle coating was stable and nontoxic to cell culture. This technology provides a means to inhibit bacterial attachment to devices attached to the eye, without damage to ocular cells.

Sorption of uranyl ions on hydrous silicon dioxide

International Nuclear Information System (INIS)

Lieser, K.H.; Quandt-Klenk, S.; Thybusch, B.

1992-01-01

Sorption of uranyl ions on SiO 2 .χH 2 O (silica gel) is investigated in absence and in presence of carbonate as function of pH. The curves obtained are very similar to those observed for sorption of uranyl ion on TiO 2 .χH 2 O, indicating the dominating influence of the uranium species in solution. Between pH 2 and 5 the sorption ratio R s increases with hydrolysis of uranyl ions (formation of UO 2 OH + ), around pH 7 it is nearly independent of pH, and at higher pH it decreases again. The equilibrium constants are calculated for these ranges. In presence of carbonate R s decreases drastically above pH 6, due to the formation of carbonato complexes in solution. Sorption of uranyl ions on SiO 2 .χH 2 O, on TiO 2 .χH 2 O, and on cryst. SiO 2 and Al 2 O 3 is compared. The problems of 'surface complexation' modelling are discussed. (orig.)

Photochemical reduction of uranyl ion with amides

International Nuclear Information System (INIS)

Brar, A.S.; Chander, R.; Sandhu, S.S.

1981-01-01

The photochemical reduction of uranyl ion by formamide, acetamide, propionamide, butyramide, iso butyramids, n-methylformamide, N, N-dimethylformamide and N, N-diethylformamide in aqueous medium using radiation >= 380 nm from a medium pressure mercury vapour lamp has been investigated. The reduction with the said amides has been found to obey pseudo first order kinetics. The magnitude of the rate of reduction for the simple amides has been found to follow the following order formamide > isobutyramide approx. butyramide > propionamide > acetamide while the rate order for N-alkylformamides compared with that of the formamide has been found to be formamide > N-methylformamide > N,N-diethylformamide approx. N,N-dimethylformamide. The pseudo first order rate constants and quenching constants have been found from the kinetic data. It has been found that physical and chemical quenching compete with each other. Plots of reciprocal of quantum yields versus reciprocal [amide] have been found to be linear with intercepts on the ordinate axis. Absorption spectra of uranyl ion in doubly distilled water, in the presence of acid and in the presence of acid and amide reveal that there is no ground state interaction between uranyl ion and the amide. A mechanism of photoreduction of uranyl ion with amides has been proposed. (author)

Technological applications of organo-montmorillonites in the removal of pyrimethanil from water: adsorption/desorption and flocculation studies.

Science.gov (United States)

Flores, Federico M; Undabeytia, Tomas; Morillo, Esmeralda; Torres Sánchez, Rosa M

2017-06-01

Pyrimethanil (2-aniline-4, 6-dimethylpyrimidine, PRM) is used in fruit packing plants to control fungal infections and diseases. The effluents greatly polluted with this fungicide, as a point source contamination, need to be technologically treated for their regeneration before they reach water bodies. This work evaluates the use of organo-montmorillonites, synthetized in our laboratory, for their application in adsorption and coagulation/flocculation processes for the removal of PRM from water. The adsorption-desorption performance of PRM in a raw montmorillonite (Mt) and several organo-montmorillonites (organo-Mt) obtained by different amounts and types of exchanged surfactants (octadecyltrimethylammonium (ODTMA) and didodecyldimethylammonium (DDAB) bromides and benzyltrimethylammonium chloride (BTMA)) was studied. The PRM adsorption on raw Mt was assigned mainly to an interlayer occupancy, while hydrophobic interactions between PRM and the surfactants in the exchanged samples increased PRM adsorption, which was correlated with the surfactant loading. PRM desorption showed irreversible behavior in raw Mt, which changed to reversible for organo-Mt samples, and was also correlated with the increase of surfactant loading.Two of the organo-Mt with high surfactant loading (twice the CEC) were assayed for the removal of commercial PRM in coagulation/flocculation tests, and their performance was compared to that of the native clay (Mt). The use of the organo-Mt produced flocculation at a very low ratio (0.5 g L -1 ), whereas no flocculation was observed with Mt. These results proved the feasibility of the use of organo-Mt for the treatment of wastewater contaminated with PRM using a low organo-Mt/liquid ratio.

Evaluation of the stability of uranyl peroxo-carbonato complex ions in carbonate media at different temperatures

Energy Technology Data Exchange (ETDEWEB)

Kim, Kwang-Wook, E-mail: nkwkim@kaeri.re.kr [Korea Atomic Energy Research Institute, 1045 Daedeok daero, Yuseong, Daejeon 305-353 (Korea, Republic of); Lee, Keun-Young; Chung, Dong-Yong; Lee, Eil-Hee; Moon, Jei-Kwon [Korea Atomic Energy Research Institute, 1045 Daedeok daero, Yuseong, Daejeon 305-353 (Korea, Republic of); Shin, Dong-Woo [Gyeongsang National University, 900 Gajwa, Jinju 660-701 (Korea, Republic of)

2012-09-30

Highlights: Black-Right-Pointing-Pointer The stability of peroxide in uranyl peroxo carbonato complex solutions with different temperatures was characterized. Black-Right-Pointing-Pointer The decomposition rate of uranyl peroxo carbonato complex ion to uranyl tris-carbonato complex ion was observed to increase with temperature Black-Right-Pointing-Pointer The decomposition kinetics of uranyl peroxo carbonato complex ions was evaluated by absorption and Raman spectroscopies. Black-Right-Pointing-Pointer A precipitate of uranyl peroxo carbonato complex solution was evaluated with XRD. - Abstract: This work studied the stability of peroxide in uranyl peroxo carbonato complex ions in a carbonate solution with hydrogen peroxide using absorption and Raman spectroscopies, and evaluated the temperature dependence of the decomposition characteristics of uranyl peroxo carbonato complex ions in the solution. The uranyl peroxo carbonato complex ions self-decomposed more rapidly into uranyl tris-carbonato complex ions in higher temperature carbonate solutions. The concentration of peroxide in the solution without free hydrogen peroxide represents the concentration of uranyl peroxo carbonato complex ions in a mixture of uranyl peroxo carbonato complex and uranyl tris-carbonato complex ions. The self-decomposition of the uranyl peroxo carbonato complex ions was a first order reaction, and its activation energy was evaluated to be 7.144 Multiplication-Sign 10{sup 3} J mol{sup -1}. The precipitation of sodium uranium oxide hydroxide occurred when the amount of uranyl tris-carbonato complex ions generated from the decomposition of the uranyl peroxo carbonato complex ions exceeded the solubility of uranyl tris-carbonato ions in the solution at the solution temperature.

Uranium and selenium resistance in Cupriavidus metallidurans CH34

International Nuclear Information System (INIS)

Avoscan, L.; Untereiner, G.; Carriere, M.; Gouget, B.; Degrouard, J.

2007-01-01

Cupriavidus metallidurans CH34, a soil bacterium, is known to resist a variety of heavy metals and metalloids. Its capacity to resist, accumulate and transform selenium (Se as selenite or selenate) and uranium (U as uranyl-carbonate and uranyl-citrate) was investigated. C. metallidurans CH34 resists to high U concentrations (up to 10 mM) whatever its speciation. However, no major accumulation could be measured: U-carbonate and U-citrate are not bio-available for the bacteria. The anaerobic response of C. metallidurans CH34 to U will be looked for. C. metallidurans CH34 resists to high Se concentrations (up to 4 mM of selenite and 8 mM of selenate). Bacteria exposed to 2 mM of selenite accumulate 25 times more Se than when they are exposed to same concentration of selenate. Se resistance is characterized by the reduction of oxy-anions in the bacteria. Selenite is reduced to elemental Se by an intracellular process, but the metabolic fate of selenate is unknown. By combining three methods of speciation (X-ray absorption spectroscopy (XANES and EXAFS), HPLC-ICP-MS and SDS-PAGE coupled with particle induced X-ray emission (PIXE)), we both identified and specified the chemical intermediates formed by this bacterium upon exposure to these oxy-anions. Two mechanisms of reduction of Se oxides in C. metallidurans CH34 were highlighted. Assimilation transforms selenite and selenate into organic Se, identified as seleno-methionine and leads to its non-specific incorporation into bacterial proteins (presence of selenious proteins). Detoxication precipitates selenite in nano-particles of elemental Se. (authors)

The influence of temperature on selenate adsorption by goethite

Energy Technology Data Exchange (ETDEWEB)

Kersten, M.; Vlasova, N. [Mainz Univ. (Germany). Geosciences Inst.

2013-08-01

Acid-base batch titration data up to 75 C were used to constrain a temperature-dependent 1-pK basic Stern model of the surface protonation reactions of goethite. Experimental data for the temperature dependence of pH{sub PZC} (as determined using the two-term Van't Hoff extrapolation) yielded a negative value of -44.9 kJ/mol for the surface protonation enthalpy, and therefore a shift of the zero point of charge towards lower pH values with increasing temperature. Batch titrations at selenate concentrations of between 10 and 100 {mu}M showed an increased degree of adsorption in the acidic pH range, which appeared to be sensitive to the ionic strength of the solution. The selenate adsorption edges shifted towards more acidic pH values with increasing temperature. A 1-pK charge distribution multi-site surface complexation (CD-MUSIC) model was applied, assuming the formation of an outer-spheric surface complex together with an inner-spheric one, in agreement with published spectroscopic information. The temperature behaviour of the intrinsic equilibrium constants were well represented by a linear Van't Hoff log K vs. 1/T plot, from which negative enthalpy values could be derived for both adsorption reactions. The adsorption of the selenate was therefore exothermic and became weaker with increasing temperature. The bidentate inner-spheric complex was more sensitive to rises in temperature (-70 kJ/mol), compared to the outer-spheric complex (-36 kJ/mol). The latter ultimately became the dominating adsorption process at the highest temperature studied. (orig.)

The influence of temperature on selenate adsorption by goethite

International Nuclear Information System (INIS)

Kersten, M.; Vlasova, N.

2013-01-01

Acid-base batch titration data up to 75 C were used to constrain a temperature-dependent 1-pK basic Stern model of the surface protonation reactions of goethite. Experimental data for the temperature dependence of pH PZC (as determined using the two-term Van't Hoff extrapolation) yielded a negative value of -44.9 kJ/mol for the surface protonation enthalpy, and therefore a shift of the zero point of charge towards lower pH values with increasing temperature. Batch titrations at selenate concentrations of between 10 and 100 μM showed an increased degree of adsorption in the acidic pH range, which appeared to be sensitive to the ionic strength of the solution. The selenate adsorption edges shifted towards more acidic pH values with increasing temperature. A 1-pK charge distribution multi-site surface complexation (CD-MUSIC) model was applied, assuming the formation of an outer-spheric surface complex together with an inner-spheric one, in agreement with published spectroscopic information. The temperature behaviour of the intrinsic equilibrium constants were well represented by a linear Van't Hoff log K vs. 1/T plot, from which negative enthalpy values could be derived for both adsorption reactions. The adsorption of the selenate was therefore exothermic and became weaker with increasing temperature. The bidentate inner-spheric complex was more sensitive to rises in temperature (-70 kJ/mol), compared to the outer-spheric complex (-36 kJ/mol). The latter ultimately became the dominating adsorption process at the highest temperature studied. (orig.)

Aggregation-induced emission active tetraphenylethene-based sensor for uranyl ion detection.

Science.gov (United States)

Wen, Jun; Huang, Zeng; Hu, Sheng; Li, Shuo; Li, Weiyi; Wang, Xiaolin

2016-11-15

A novel tetraphenylethene-based fluorescent sensor, TPE-T, was developed for the detection of uranyl ions. The selective binding of TPE-T to uranyl ions resulted in a detectable signal owing to the quenching of its aggregation-induced emission. The developed sensor could be used to visually distinguish UO2(2+) from lanthanides, transition metals, and alkali metals under UV light; the presence of other metal ions did not interfere with the detection of uranyl ions. In addition, TPE-T was successfully used for the detection of uranyl ions in river water, illustrating its potential applications in environmental systems. Copyright © 2016 Elsevier B.V. All rights reserved.

The state of uranyl ions in water-dioxane solvent mixtures

International Nuclear Information System (INIS)

Geipel, G.; Nebel, D.; Baraniak, L.

1985-01-01

A comparison of the spectra of uranyl ions in HCl and dioxane solutions leads to the conclusion that dioxane promotes complex formation. The investigation of spectra showed that taking into account the hydrolysis of uranyl ions in dioxane containing solutions, two successive equilibrium reactions take place. The formation constants were determined. Conductivity measurements confirmed the spectrophotometrically determined equilibria. In solutions containing up to 60 % dioxane there is no incorporation of dioxane in the solvating envelope of the uranyl ion. (author)

Evaluation of the stability of uranyl peroxo-carbonato complex ions in carbonate media at different temperatures.

Science.gov (United States)

Kim, Kwang-Wook; Lee, Keun-Young; Chung, Dong-Yong; Lee, Eil-Hee; Moon, Jei-Kwon; Shin, Dong-Woo

2012-09-30

This work studied the stability of peroxide in uranyl peroxo carbonato complex ions in a carbonate solution with hydrogen peroxide using absorption and Raman spectroscopies, and evaluated the temperature dependence of the decomposition characteristics of uranyl peroxo carbonato complex ions in the solution. The uranyl peroxo carbonato complex ions self-decomposed more rapidly into uranyl tris-carbonato complex ions in higher temperature carbonate solutions. The concentration of peroxide in the solution without free hydrogen peroxide represents the concentration of uranyl peroxo carbonato complex ions in a mixture of uranyl peroxo carbonato complex and uranyl tris-carbonato complex ions. The self-decomposition of the uranyl peroxo carbonato complex ions was a first order reaction, and its activation energy was evaluated to be 7.144×10(3) J mol(-1). The precipitation of sodium uranium oxide hydroxide occurred when the amount of uranyl tris-carbonato complex ions generated from the decomposition of the uranyl peroxo carbonato complex ions exceeded the solubility of uranyl tris-carbonato ions in the solution at the solution temperature. Copyright © 2012 Elsevier B.V. All rights reserved.

Structure and dynamics of aqueous solution of uranyl ions

International Nuclear Information System (INIS)

Chopra, Manish; Choudhury, Niharendu

2014-01-01

The present work describes a molecular dynamics simulation study of structure and dynamics of aqueous solution of uranyl ions in water. Structural properties of the system in terms of radial distribution functions and dynamical characteristics as obtained through velocity autocorrelation function and mean square displacements have been analyzed. The results for radial distribution functions show the oxygen of water to form the first solvation shell at 2.4 Å around the uranium atom, whereas the hydrogen atoms of water are distributed around the uranium atom with the major peak at around 3.0 Å. Analyses of transport behaviors of ions and water through MSD indicates that the diffusion of the uranyl ion is much less as compared to that of the water molecules. It is also observed that the dynamical behavior of water molecules gets modified due to the presence of uranyl ion. The effect of increase in concentration of uranyl ions on the structure and dynamics of water molecules is also studied

Comparative study of uranyl(VI) and -(V) carbonato complexes in an aqueous solution.

Science.gov (United States)

Ikeda, Atsushi; Hennig, Christoph; Tsushima, Satoru; Takao, Koichiro; Ikeda, Yasuhisa; Scheinost, Andreas C; Bernhard, Gert

2007-05-14

Electrochemical, complexation, and electronic properties of uranyl(VI) and -(V) carbonato complexes in an aqueous Na2CO3 solution have been investigated to define the appropriate conditions for preparing pure uranyl(V) samples and to understand the difference in coordination character between UO22+ and UO2+. Cyclic voltammetry using three different working electrodes of platinum, gold, and glassy carbon has suggested that the electrochemical reaction of uranyl(VI) carbonate species proceeds quasi-reversibly. Electrolysis of UO22+ has been performed in Na2CO3 solutions of more than 0.8 M with a limited pH range of 11.7 < pH < 12.0 using a platinum mesh electrode. It produces a high purity of the uranyl(V) carbonate solution, which has been confirmed to be stable for at least 2 weeks in a sealed glass cuvette. Extended X-ray absorption fine structure (EXAFS) measurements revealed the structural arrangement of uranyl(VI) and -(V) tricarbonato complexes, [UO2(CO3)3]n- [n = 4 for uranyl(VI), 5 for uranyl(V)]. The bond distances of U-Oax, U-Oeq, U-C, and U-Odist are determined to be 1.81, 2.44, 2.92, and 4.17 A for the uranyl(VI) complex and 1.91, 2.50, 2.93, and 4.23 A for the uranyl(V) complex, respectively. The validity of the structural parameters obtained from EXAFS has been supported by quantum chemical calculations for the uranyl(VI) complex. The uranium LI- and LIII-edge X-ray absorption near-edge structure spectra have been interpreted in terms of electron transitions and multiple-scattering features.

Solid solutions of hydrogen uranyl phosphate and hydrogen uranyl arsenate. A family of luminescent, lamellar hosts

International Nuclear Information System (INIS)

Dorhout, P.K.; Rosenthal, G.L.; Ellis, A.B.

1988-01-01

Hydrogen uranyl phosphate, HUO 2 PO 4 x 4H 2 O (HUP), and hydrogen uranyl arsenate, HUO 2 AsO 4 x 4H 2 O (HUAs), form solid solutions of composition HUO 2 (PO 4 ) 1-x (AsO 4 )x (HUPAs), representing a family of lamellar, luminescent solids that can serve as hosts for intercalation chemistry. The solids are prepared by aqueous precipitation reactions from uranyl nitrate and mixtures of phosphoric and arsenic acids; thermogravimetric analysis indicates that the phases are tetrahydrates, like HUP and HUAs. Powder x-ray diffraction data reveal the HUPAs solids to be single phases whose lattice constants increase with X, in rough accord with Vegard's law Spectral shifts observed for the HUPAs samples. Emission from the solids is efficient (quantum yields of ∼ 0.2) and long-lived (lifetimes of ∼ 150 μs), although the measured values are uniformly smaller than those of HUP and HUAs; unimolecular radiative and nonradiative rate constants for excited-state decay of ∼ 1500 and 5000 s -1 , respectively, have been calculated for the compounds. 18 refs., 5 figs., 2 tabs

Thermal decomposition of uranyl sulphate hydrate

International Nuclear Information System (INIS)

Sato, T.; Ozawa, F.; Ikoma, S.

1980-01-01

The thermal decomposition of uranyl sulphate hydrate (UO 2 SO 4 .3H 2 O) has been investigated by thermogravimetry, differential thermal analysis, X-ray diffraction and infrared spectrophotometry. As a result, it is concluded that uranyl sulphate hydrate decomposes thermally: UO 2 SO 4 .3H 2 O → UO 2 SO 4 .xH 2 O(2.5 = 2 SO 4 . 2H 2 O → UO 2 SO 4 .H 2 O → UO 2 SO 4 → α-UO 2 SO 4 → β-UO 2 SO 4 → U 3 O 8 . (author)

Structural contributions to the third-law entropy of uranyl phases

International Nuclear Information System (INIS)

Chen, F.; Ewing, R.C.

1999-01-01

Entropies that are used in geochemical calculations are usually based on calorimetric measurements. However, because of the contributions of neglected residual entropies which cannot be determined by calorimetric measurements, the true third-law entropies for many phases may be quite different from those derived from thermal data. The residual entropies are caused by site-mixing, structural disorder and magnetic spin disorder and may result in a considerable contribution to the third-law entropy of solid phases. Magnetic spin-configurational entropy is not expected to be significant in uranyl phases. However, because most uranyl phases are based on sheet or chain structures and usually contain several molecular water groups, site-mixing, vacancies, as well as disorder in the orientation of hydrogen bonds and the polar H 2 O molecules may occur. Calculations of the ideal site-mixing configurational entropy for some uranyl phases indicate that the residual contributions that arise from substitution and vacancies to the third-law entropies of uranyl phases may be large. A brief examination of the crystal chemistry of water molecules in uranyl phases suggests that considerable residual entropy may be caused by the disorder of hydrogen bonds associated with interstitial H 2 O groups

Structure, vibrations and quantum chemical investigations of hydrogen bonded complex of bis(1-hydroxy-2-methylpropan-2-aminium)selenate

Science.gov (United States)

Thirunarayanan, S.; Arjunan, V.; Marchewka, M. K.; Mohan, S.

2017-04-01

The hydrogen bonded molecular complex bis(1-hydroxy-2-methylpropan-2-aminium)selenate (C8H24N2O6Se) has been prepared by the reaction of 2-amino-2-methyl propanol and selenic acid. The X-ray diffraction analysis revealed that the intermolecular proton transfer from selenic acid (SeO4H2) to 2-amino-2-methylpropanol results in the formation of bis(1-hydroxy-2-methylpropan-2-aminium)selenate (HMPAS) salt and the fragments are connected through H-bonding and ion pairing. The N-H⋯O and O-H⋯O interactions between 2-amino-2-methylpropanol and selenic acid determine the supramolecular arrangement in three-dimensional space. The salt crystallises in the space group P121/n1 of monoclinic system. The complete vibrational assignments of HMPAS have been performed by FTIR and FT-Raman spectroscopy. The experimental data are correlated with the structural properties namely the energy, thermodynamic parameters, atomic charges, hybridization concepts and vibrational frequencies determined by quantum chemical studies performed with B3LYP method using 6-311++G*, 6-31+G* and 6-31G** basis sets.

Use of uranyl nitrate as a shift reagent in polar and inert solvents

International Nuclear Information System (INIS)

Nosov, B.P.

1988-01-01

This work examines the effect of uranyl nitrate as a shift reagent on the PMR spectra of different organic molecules in polar and inert solvents. In order to identify the coordination site of the uranyl ion, its effect on the spectra of amino acids and acetic or propionic acids in water was compared. It was found that the induced shifts of the protons in the corresponding positions of the different acids after addition of uranyl nitrate agreed to within ±0.01 ppm. When nitrogenous bases such as diethylamine and pyridine were added to solutions of the carboxylic acids with uranyl nitrate, an increase in the induced chemical shift of the resonance signals occurred. These facts suggest the coordination of the uranyl ion with the carboxyl oxygen both for acetic and propionic acids and for amino acids. The authors established that the addition of uranyl nitrate to solutions of organic compounds caused different downfield shifts of the resonance signals from the protons. In polar solvents shifts induced by uranyl nitrate in the PMR spectra of carboxylic acids occur only when nitrogenous bases are added

A study of precipitation from pure solutions of uranyl nitrate; Etude de la precipitaion de solutions pures de nitrate d'uranyle

Energy Technology Data Exchange (ETDEWEB)

Decrop, J; Holder, J; Sauteron, J [Commissariat a l' Energie Atomique, Usine du Bouchet, Service des Lab. de Recherches et de Controle, Saclay (France). Centre d' Etudes Nucleaires

1961-07-01

After its purification by extraction of the uranyl nitrate from the organic solvent, uranium has to be converted into solid form again: uranium trioxide (UO{sub 3}). It can be done either by thermal decomposition of uranyl nitrate or by precipitation of uranium, followed by filtration and calcination. Only the second method has been studied for now at the Bouchet plant. This paper reports the bench-scale and pilot-scale experiments of the studies of the precipitation of pure solutions of uranyl nitrate using ammonia (gaseous or in solution) or ammonium carbonate. These have been carried out at the Bouchet plant. It investigates the chemical aspect (pH, precipitates chemical composition) and the technical aspect of the different ways of precipitation (conditions of precipitation, decantation and filtration of precipitates). (M.P.)

Hydrothermal Phase Relations Among Uranyl Minerals at the Nopal I Analog Site

International Nuclear Information System (INIS)

Murphy, William M.

2007-01-01

Uranyl mineral paragenesis at Nopal I is an analog of spent fuel alteration at Yucca Mountain. Petrographic studies suggest a variety of possible hydrothermal conditions for uranium mineralization at Nopal I. Calculated equilibrium phase relations among uranyl minerals show uranophane stability over a broad range of realistic conditions and indicate that uranyl mineral variety reflects persistent chemical potential heterogeneity. (author)

Global Lunar Gravity Field Determination Using Historical and Recent Tracking Data in Preparation for SELENE

Science.gov (United States)

Goossens, S.; Matsumoto, K.; Namiki, N.; Hanada, H.; Iwata, T.; Tsuruta, S.; Kawano, N.; Sasaki, S.

2006-12-01

In the near future, a number of satellite missions are planned to be launched to the Moon. These missions include initiatives by China, India, the USA, as well as the Japanese SELENE mission. These missions will gather a wealth of lunar data which will improve the knowledge of the Moon. One of the main topics to be addressed will be the lunar gravity field. Especially SELENE will contribute to improving the knowledge of the gravity field, by applying 4-way Doppler tracking between the main satellite and a relay satellite, and by applying a separate differential VLBI experiment. These will improve the determination of the global gravity field, especially over the far side and at the lower degrees (mostly for degrees lower than 30), as is shown by extensive simulations of the SELENE mission. This work focuses on the determination of the global lunar gravity field from all available tracking data to this date. In preparation for the SELENE mission, analysis using Lunar Prospector tracking data, as well as Clementine data and historical data from the Apollo and Lunar Orbiter projects is being conducted at NAOJ. Some SMART-1 tracking data are also included. The goal is to combine the good-quality data from the existing lunar missions up to this date with the tracking data from SELENE in order to derive a new lunar gravity field model. The focus therefore currently lies on processing the available data and extracting lunar gravity field information from them. It is shown that the historical tracking data contribute especially to the lower degrees of the global lunar gravity field model. Due to the large gap in tracking data coverage over the far side for the historical data, the higher degrees are almost fully determined by the a priori information in the form of a Kaula rule. The combination with SELENE data is thus expected to improve the estimate for the lower degrees even further, including coverage of the far side. Since historical tracking data are from orbits with

Determination of iodide, iodate and organo-iodine in waters with a new total organic iodine measurement approach.

Science.gov (United States)

Gong, Tingting; Zhang, Xiangru

2013-11-01

The dissolved iodine species that dominate aquatic systems are iodide, iodate and organo-iodine. These species may undergo transformation to one another and thus affect the formation of iodinated disinfection byproducts during disinfection of drinking waters or wastewater effluents. In this study, a fast, sensitive and accurate method for determining these iodine species in waters was developed by derivatizing iodide and iodate to organic iodine and measuring organic iodine with a total organic iodine (TOI) measurement approach. Within this method, organo-iodine was determined directly by TOI measurement; iodide was oxidized by monochloramine to hypoiodous acid and then hypoiodous acid reacted with phenol to form organic iodine, which was determined by TOI measurement; iodate was reduced by ascorbic acid to iodide and then determined as iodide. The quantitation limit of organo-iodine or sum of organo-iodine and iodide or sum of organo-iodine, iodide and iodate was 5 μg/L as I for a 40 mL water sample (or 2.5 μg/L as I for an 80 mL water sample, or 1.25 μg/L as I for a 160 mL water sample). This method was successfully applied to the determination of iodide, iodate and organo-iodine in a variety of water samples, including tap water, seawater, urine and wastewater. The recoveries of iodide, iodate and organo-iodine were 91-109%, 90-108% and 91-108%, respectively. The concentrations and distributions of iodine species in different water samples were obtained and compared. Copyright © 2013 Elsevier Ltd. All rights reserved.

Syntheses and crystal structures of two novel alkaline uranyl chromates A2(UO2)(CrO4)2 (A=Rb, Cs) with bidentate coordination mode of uranyl ions by chromate anions

International Nuclear Information System (INIS)

Siidra, Oleg I.; Nazarchuk, Evgeny V.; Krivovichev, Sergey V.

2012-01-01

Single crystals of Cs 2 (UO 2 )(CrO 4 ) 2 and Rb 2 (UO 2 )(CrO 4 ) 2 were prepared by solid state reactions. The structures are based upon the [(UO 2 )(CrO 4 ) 2 ] 2− chains. Within the chains, UrO 5 pentagonal bipyramids (Ur=uranyl) form Ur 2 O 8 dimers, which are linked via CrO 4 tetrahedra into one-dimensional chains. The CrO 4 tetrahedra coordinate uranyl ions in both mono- and bidentate fashion, which is unusual for uranyl chromates. The bidentate coordination has a strong influence upon geometrical parameters of both U and Cr coordination polyhedra. The conformation of the chains in 1 and 2 is different due to the different size of the Cs + and Rb + cations. - Graphical abstract: Uranyl chromate chain with monodentate and bidentate coordination mode of uranyl cations by CrO 4 tetrahedra in Cs 2 (UO 2 )(CrO 4 ) 2 . Highlights: ► Single crystals of novel uranyl chromates were prepared by solid state reactions. ► The CrO 4 tetrahedra coordinate uranyl ions in both mono- and bidentate fashion. ►The bidentate coordination has a strong influence upon geometrical parameters.

Density functional study of uranyl (VI) amidoxime complexes

International Nuclear Information System (INIS)

Chi Fang-Ting; Xiong Jie; Hu Sheng; Xia Xiu-Long; Wang Xiao-Lin; Li Peng; Gao Tao

2012-01-01

Uranyl (VI) amidoxime complexes are investigated using relativistic density functional theory. The equilibrium structures, bond orders, and Mulliken populations of the complexes have been systematically investigated under a generalized gradient approximation (GGA). Comparison of (acet) uranyl amidoxime complexes ([UO 2 (AO) n ] 2−n , 1 ≤ n ≤ 4) with available experimental data shows an excellent agreement. In addition, the U−O(1), U−O(3), C(1)−N(2), and C(3)−N(4) bond lengths of [UO 2 (CH 3 AO) 4 ] 2− are longer than experimental data by about 0.088, 0.05, 0.1, and 0.056 Å. The angles of N(3)−O(3)−U, O(2)−N(1)−C(1), N(3)−C(3)−N(4), N(4)−C(3)−C(4), and C(4)−C(3)−N(3) are different from each other, which is due to existing interaction between oxygen in uranyl and hydrogen in amino group. This interaction is found to be intra-molecular hydrogen bond. Studies on the bond orders, Mulliken charges, and Mulliken populations demonstrate that uranyl oxo group functions as hydrogen-bond acceptors and H atoms in ligands act as hydrogen-bond donors forming hydrogen bonds within the complex

Optimum Exploration for the Self-Ordering of Anodic Porous Alumina Formed via Selenic Acid Anodizing

OpenAIRE

Akiya, Shunta; Kikuchi, Tatsuya; Natsui, Shungo; Suzuki, Ryosuke O.

2015-01-01

Improvements of the regularity of the arrangement of anodic porous alumina formed by selenic acid anodizing were investigated under various operating conditions. The oxide burning voltage increased with the stirring rate of the selenic acid solution, and the high applied voltage without oxide burning was achieved by vigorously stirring the solution. The regularity of the porous alumina was improved as the anodizing time and surface flatness increased. Conversely, the purity of the 99.5–99.999...

Theoretical insights into the uranyl adsorption behavior on vanadium carbide MXene

Science.gov (United States)

Zhang, Yu-Juan; Zhou, Zhang-Jian; Lan, Jian-Hui; Ge, Chang-Chun; Chai, Zhi-Fang; Zhang, Peihong; Shi, Wei-Qun

2017-12-01

Remediation of the contamination by long-lived actinide wastes is extremely important but also challenging. Adsorption based techniques have attracted much research attention for their potential as low-cost and effective methods to reduce the radioactive waste from solution. In this work, we have investigated the adsorption behavior of uranyl species [with the general form UO2(L1)x(L2)y(L3)z, where L1, L2 and L3 stand for ligands H2O, OH and CO3, respectively] on hydroxylated vanadium carbide V2C(OH)2 MXene nanosheets using density functional theory based simulation methods We find that all studied uranyl species can stably bond to hydroxylated MXene with binding energies ranging from -3.3 to -4.6 eV, suggesting that MXenes could be effective adsorbers for uranyl ions. The strong adsorption is achieved by forming two Usbnd O bonds with the hydroxylated Mxene. In addition, the axial oxygen atoms from the uranyl ions form hydrogen bonds with the hydroxylated V2C, further strengthening the adsorption. We have also investigated the effects of F termination on the uranyl adsorption properties of V2C nanosheets. Usbnd F bonds are in general weaker than Usbnd O bonds on the adsorption site, suggesting that F terminated Mexne is less favorable for uranyl adsorption applications.

Thermal degradation of organo-soluble polyimides

Institute of Scientific and Technical Information of China (English)

黄俐研; 史燚; 金熹高

1999-01-01

The thermal degradation behavior of two organo-soluble polyimides was investigated by high resolution pyrolysis-gas chromatography/mass spectrometry. The pyrolyzates of the polymers at various temperatures were identified and characterized quantitatively. The relationship between the polymer structure and pyrolyzate distribution was discussed. The kinetic parameters of the thermal degradation were calculated based on thermogravimetric measurements. Finally, the thermal degradation mechanism for the polymers was suggested.

Probing uranyl(VI) speciation in the presence of amidoxime ligands using electrospray ionization mass spectrometry.

Science.gov (United States)

Mustapha, Adetayo M; Pasilis, Sofie P

2013-10-15

Extraction processes using poly(acrylamidoxime) resins are being developed to extract uranium from seawater. The main complexing agents in these resins are thought to be 2,6-dihydroxyiminopiperidine (DHIP) and N(1),N(5)-dihydroxypentanediimidamide (DHPD), which form strong complexes with uranyl(VI) at the pH of seawater. It is important to understand uranyl(VI) speciation in the presence of these and similar amidoxime ligands to understand factors affecting uranyl(VI) adsorption to the poly(acrylamidoxime) resins. Experiments were carried out in positive ion mode on a quadrupole ion trap mass spectrometer equipped with an electrospray ionization source. The ligands investigated were DHIP, DHPD, and N(1),N(2)-dihydroxyethanediimidamide (DHED). DHED and DHPD differ only in the number of carbons separating the oxime groups. The effects on the mass spectra of changes in uranyl(VI):ligand ratio, pH, and ligand type were examined. DHIP binds uranyl(VI) more effectively than DHPD or DHED in the pH range investigated, forming ions derived from solution-phase species with uranyl(VI):DHIP stoichiometries of 1:1, 1:2, and 2:3. The 2:3 uranyl(VI):DHIP complex appears to be a previously undescribed solution species. Ions related to uranyl(VI):DHPD complexes were detected in very low abundance. DHED is a more effective complexing agent for uranyl(VI) than DHPD, forming ions having uranyl(VI):DHED stoichiometries of 1:1, 1:2, 1:3, and 2:3. This study presents a first look at the solution chemistry of uranyl(VI)-amidoxime complexes using electrospray ionization mass spectrometry. The appearance of previously undescribed solution species suggests that the uranyl-amidoxime system is a rich and relatively complex one, requiring a more in-depth investigation. Copyright © 2013 John Wiley & Sons, Ltd.

Extraction of uranyl sulfate with primary amine

International Nuclear Information System (INIS)

Mrnka, M.; Bizek, V.; Nekovar, P.; Cizevska, S.; Schroetterova, D.

1984-01-01

PRIMENE JM-T was used for extraction. Its composition was found to approach the general formula C 21 H 43 NH 2 . It was found that the extraction of uranyl sulfate is lower in case of a higher steady-state concentration of sulfuric acid in the aqueous phase. Extraction is accompanied with coextraction of water. The results obtained showed that uranyl sulfate passes into the organic phase by two mechanisms: extraction with amine sulfate and extraction with free amine. A mathematical description of the process was made based on the obtained results. (E.S.)

Variation in electrical properties of gamma irradiated cadmium selenate nanowires

Science.gov (United States)

Chauhan, R. P.; Rana, Pallavi; Narula, Chetna; Panchal, Suresh; Choudhary, Ritika

2016-07-01

Preparation of low-dimensional materials attracts more and more interest in the last few years, mainly due to the wide field of potential commercial applications ranging from life sciences, medicine and biotechnology to communication and electronics. One-dimensional systems are the smallest dimension structures that can be used for efficient transport of electrons and thus expected to be critical to the function and integration of nanoscale devices. Nanowires with well controlled morphology and extremely high aspect ratio can be obtained by replicating a nanoporous polymer ion-track membrane with cylindrical pores of controlled dimensions. With this technique, materials can be deposited within the pores of the membrane by electrochemical reduction of the desired ion. In the present study, cadmium selenate nanowires were synthesized potentiostatically via template method. These synthesized nanowires were then exposed to gamma rays by using a 60Co source at the Inter University Accelerator Centre, New Delhi, India. Structural, morphological, electrical and elemental characterizations were made in order to analyze the effect of gamma irradiation on the synthesized nanowires. I-V measurements of cadmium selenate nanowires, before and after irradiation were made with the help of Keithley 2400 source meter and Ecopia probe station. A significant change in the electrical conductivity of cadmium selenate nanowires was found after gamma irradiation. The crystallography of the synthesized nanowires was also studied using a Rigaku X-ray diffractrometer equipped with Cu-Kα radiation. XRD patterns of irradiated samples showed no variation in the peak positions or phase change.

Variation in electrical properties of gamma irradiated cadmium selenate nanowires

Energy Technology Data Exchange (ETDEWEB)

Chauhan, R.P., E-mail: chauhanrpc@gmail.com; Rana, Pallavi, E-mail: prana.phy@gmail.com; Narula, Chetna; Panchal, Suresh; Choudhary, Ritika

2016-07-15

Preparation of low-dimensional materials attracts more and more interest in the last few years, mainly due to the wide field of potential commercial applications ranging from life sciences, medicine and biotechnology to communication and electronics. One-dimensional systems are the smallest dimension structures that can be used for efficient transport of electrons and thus expected to be critical to the function and integration of nanoscale devices. Nanowires with well controlled morphology and extremely high aspect ratio can be obtained by replicating a nanoporous polymer ion-track membrane with cylindrical pores of controlled dimensions. With this technique, materials can be deposited within the pores of the membrane by electrochemical reduction of the desired ion. In the present study, cadmium selenate nanowires were synthesized potentiostatically via template method. These synthesized nanowires were then exposed to gamma rays by using a {sup 60}Co source at the Inter University Accelerator Centre, New Delhi, India. Structural, morphological, electrical and elemental characterizations were made in order to analyze the effect of gamma irradiation on the synthesized nanowires. I–V measurements of cadmium selenate nanowires, before and after irradiation were made with the help of Keithley 2400 source meter and Ecopia probe station. A significant change in the electrical conductivity of cadmium selenate nanowires was found after gamma irradiation. The crystallography of the synthesized nanowires was also studied using a Rigaku X-ray diffractrometer equipped with Cu-Kα radiation. XRD patterns of irradiated samples showed no variation in the peak positions or phase change.

Background electrolytes and pH effects on selenate adsorption using iron-impregnated granular activated carbon and surface binding mechanisms.

Science.gov (United States)

Zhang, Ning; Gang, Daniel Dianchen; McDonald, Louis; Lin, Lian-Shin

2018-03-01

Iron-impregnated granular activated carbon (Fe-GAC) has been shown effective for selenite adsorptive removal from aqueous solutions, but similar effectiveness was not observed with selenate. This study examined the effects of background electrolytes and pH on selenate adsorption on to Fe-GAC, and surface bindings to elucidate the selenate adsorption mechanisms. The decrease magnitude of selenate adsorption capacity under three background electrolytes followed the order: LiCl > NaCl > KCl, as ionic strength increased from 0.01 to 0.1 M. Larger adsorption capacity differences among the three electrolytes were observed under the higher ionic strengths (0.05 and 0.1 M) than those under 0.01 M. Multiplet peak fittings of high resolution X-ray photoelectron spectra for O1s and Fe2p 3/2 indicated the presence of iron (III) on adsorbent surface. pH variations during the adsorbent preparation within 3-8 in NaCl solutions did not cause appreciable changes in the iron redox state and composition. Raman spectra showed the formation of both monodentate and bidentate inner sphere complexes under pHs adsorption under alkaline conditions. Mechanisms for monodentate and bidentate formations and a stable six-member ring structure were proposed. Two strategies were recommended for modifying Fe-GAC preparation procedure to enhance the selenate adsorption: (1) mixed-metal oxide coatings to increase the point of zero charge (pH zpc ); and (2) ferrous iron coating to initially reduce selenate followed by selenite adsorption. Copyright © 2017 Elsevier Ltd. All rights reserved.

Partitioning of uranyl between ferrihydrite and humic substances at acidic and circum-neutral pH

Science.gov (United States)

Dublet, Gabrielle; Lezama Pacheco, Juan; Bargar, John R.; Fendorf, Scott; Kumar, Naresh; Lowry, Gregory V.; Brown, Gordon E.

2017-10-01

As part of a larger study of the reactivity and mobility of uranyl (U(VI)O22+) cations in subsurface environments containing natural organic matter (NOM) and hydrous ferric oxides, we have examined the effect of reference humic and fulvic substances on the sorption of uranyl on 2-line ferrihydrite (Fh), a common, naturally occurring nano-Fe(III)-hydroxide. Uranyl was reacted with Fh at pH 4.6 and 7.0 in the presence and absence of Elliott Soil Humic Acid (ESHA) (0-835 ppm) or Suwanee River Fulvic Acid (SRFA) (0-955 ppm). No evidence was found for reduction of uranyl by either form of NOM after 24 h of exposure. The following three size fractions were considered in this study: (1) ≥0.2 μm (Fh-NOM aggregates), (2) 0.02-0.2 μm (dispersed Fh nanoparticles and NOM macro-molecules), and (3) <0.02 μm (dissolved). The extent to which U(VI) is sorbed in aggregates or dispersed as colloids was assessed by comparing U, Fe, and NOM concentrations in these three size fractions. Partitioning of uranyl between Fh and NOM was determined in size fraction (1) using X-ray absorption spectroscopy (XAS). Uranyl sorption on Fh-NOM aggregates was affected by the presence of NOM in different ways depending on pH and type of NOM (ESHA vs. SRFA). The presence of ESHA in the uranyl-Fh-NOM ternary system at pH 4.6 enhanced uranyl uptake more than the presence of SRFA. In contrast, neither form of NOM affected uranyl sorption at pH 7.0 over most of the NOM concentration range examined (0-500 ppm); at the highest NOM concentrations (500-955 ppm) uranyl uptake in the aggregates was slightly inhibited at pH 7.0, which is interpreted as being due to the dispersion of Fh aggregates. XAS at the U LIII-edge was used to characterize molecular-level changes in uranyl complexation as a result of sorption to the Fh-NOM aggregates. In the absence of NOM, uranyl formed dominantly inner-sphere, mononuclear, bidentate sorption complexes on Fh. However, when NOM concentration was increased at pH 4.6, the

Uranyl ion recovery from waste waters by microbiological collectors

International Nuclear Information System (INIS)

Cecal, Alexandru; Palamaru, Iliana; Navrotescu, Tinca

1995-01-01

This study deals with the bioaccumulation of uranyl ions from radioactive effluents by Scenedesmus quadricauda alga. From the experimental data one can observe a greater retaining capacity of uranyl ions after four days of contact time. Filtered uranium and alga content was determined by the arsenazo III spectrophotometric method. The colored compound was determined by using wavelength λ=665 nm. (authors)

Hydrothermal syntheses and characterization of uranyl tungstates with electro-neutral structural units

Energy Technology Data Exchange (ETDEWEB)

Balboni, Enrica; Burns, Peter C. [Univ. of Notre Dame, IN (United States). Dept. of Civil and Enviromental Engineering and Earth Sciences; Univ. of Notre Dame, IN (United States). Dept. of Chemistry and Biochemistry

2015-11-01

Two uranyl tungstates, (UO{sub 2})(W{sub 2}O{sub 7})(H{sub 2}O){sub 3} (1) and (UO{sub 2}){sub 3}(W{sub 2}O{sub 8})F{sub 2}(H{sub 2}O){sub 3} (2), were synthesized under hydrothermal conditions at 220 C and were structurally, chemically, and spectroscopically characterized. 1 Crystallizes in space group Pbcm, a = 6.673(5) Aa, b = 12.601(11) Aa, c = 11.552 Aa; 2 is in C2/m, a = 13.648(1) Aa, b = 16.852(1) Aa, c = 9.832(1) Aa, β = 125.980(1) {sup circle}. In 1 the U(VI) cations are present as (UO{sub 2}){sup 2+} uranyl ions that are coordinated by five oxygen atoms to give pentagonal bipyramids. These share two edges with two tungstate octahedra and single vertices with four additional octahedra, resulting in a sheet with the iriginite-type anion topology. Only water molecules are located in the interlayer. The structural units of 2 consist of (UO{sub 2}){sup 2+} uranyl oxy-fluoride pentagonal bipyramids present as either [UO{sub 2}F{sub 2}O{sub 3}]{sup -6} or [UO{sub 2}FO{sub 4}]{sup -5}, and strongly distorted tungstate octahedra. The linkage of uranyl pentagonal bipyramids and tungstate octahedra gives a unique sheet anion topology consisting of pentagons, squares and triangles. In 2, the uranyl tungstates sheets are connected into a novel electro-neutral three-dimensional framework through dimers of uranyl pentagonal bipyramids. These dimers connecting the sheets share an edge defined by F anions. 2 is the first example of a uranyl tungstate oxy-fluoride, and 1 and 2 are rare examples of uranyl compounds containing electro-neutral structural units.

Nephrotoxicity of uranyl acetate: effect on rat kidney brush border membrane vesicles

International Nuclear Information System (INIS)

Goldman, M.; Yaari, A.; Moran, A.; Doshnitzki, Z.; Cohen-Luria, R.

2006-01-01

Since the Gulf war exposure to depleted uranium, a known nephrotoxic agent, there is a renewed interest in the toxic effects of uranium in general and its mechanism of nephrotoxicity which is still largely unknown in particular. In order to investigate the mechanism responsible for uranium nephrotoxicity and the therapeutic effect of urine alkalization, we utilized rat renal brush border membrane vesicles (BBMV). Uranyl acetate (UA) caused a decrease in glucose transport in BBMV. The apparent K i of uranyl was 139±30 μg uranyl/mg protein of BBMV. Uranyl at 140 μg/mg protein of BBMV reduced the maximal capacity of the system to transport glucose [V max 2.2±0.2 and 0.96±0.16 nmol/mg protein for control and uranyl treated BBMV (P m (1.54±0.33 and 1.54±0.51 mM for control, and uranyl treated BBMV, respectively). This reduction in V max is at least partially due to a decrease in the number of sodium-coupled glucose transporters as apparent from the reduction in phlorizin binding to the uranyl treated membranes, V max was reduced from 247±13 pmol/mg protein in control BBMV to 119±3 pmol/mg protein in treated vesicles (P<0.001). The pH of the medium has a profound effect on the toxicity of UA on sodium-coupled glucose transport in BBMV: higher toxicity at neutral pH (around pH 7.0), and practically no toxicity at alkaline pH (7.6). This is the first report showing a direct inhibitory dose and pH dependent effect of uranyl on the glucose transport system in isolated apical membrane from kidney cortex. (orig.)

New insights into the acid mediated disproportionation of pentavalent uranyl

Energy Technology Data Exchange (ETDEWEB)

Mougel, Victor; Biswas, Biplab; Pecaut, Jacques; Mazzanti, Marinella [Laboratoire de Reconnaissance Ionique et Chimie de Coordination, SCIB, UMR-E 3 CEA-UJF FRE 3200 CNRS, INAC, CEA-Grenoble, 17 rue des Martyrs, 38054 Grenoble Cedex 09 (France)

2010-07-01

The reaction of benzoic acid with the uranyl(V) complex [(UO{sub 2}Py{sub 5})(KI{sub 2}Py{sub 2})] in pyridine leads to immediate disproportionation with formation of a hexa-nuclear U(IV) benzoate cluster, a bis-benzoate complex of uranyl(VI) and water. (authors)

Thermochemical investigations on uranyl phosphates and arsenates

International Nuclear Information System (INIS)

Barten, H.

1986-01-01

Results are described of a study of the thermochemical stability of anhydrous phosphates and arsenates. The results of phase studies deal with compound formation and characterization, coexisting phases and limiting physical or chemical properties. The uranyl phosphates evolve oxygen at higher temperatures and the arsenates lose arsenic oxide vapour. These phenomena give the possibility to describe their thermodynamic stabilities. Thus oxygen pressures of uranyl phosphates have been measured using a static, non-isothermal method. Having made available the pure anhydrous compounds in the course of this investigation, molar thermodynamic quantities have been measured as well. These include standard enthalpies of formation from solution calorimetry and high-temperature heat-capacity functions derived from enthalpy increments measured. Some attention is given to compounds with uranium in valencies lower than six which have been met during the investigation. An evaluation is made of the thermodynamics of the compounds studied, to result in tabulized high-temperature thermodynamic functions. Relative stabilities within the systems are discussed and comparisons of the uranyl phosphates and the arsenates are made. (Auth.)

The application of time-resolved luminescence spectroscopy to a remote uranyl sensor

International Nuclear Information System (INIS)

Varineau, P.T.; Duesing, R.; Wangen, L.E.

1991-01-01

Time resolved luminescence spectroscopy is an effective method for the determination of a wide range of uranyl concentrations in aqueous samples. We have applied this technique to the development of a remote sensing device using fiber optic cables coupled with a micro flow cell in order to probe for uranyl in aqueous samples. This sensor incorporates a Nafion membrane through which UO 2 2+ can diffuse in to a reaction/analysis chamber which holds phosphoric acid, a reagent which enhances the uranyl luminescence intensity and lifetime. With this device, anionic and fluorescing organic interferences could be eliminated, allowing for the determination of uranyl over a concentration range of 10 4 to 10 -9 M. 17 refs., 5 figs

Synthesis of uranyl ion imprinted polymer and its application in analysis

International Nuclear Information System (INIS)

Xiao Jingshui; Liu Huijun; Xiao Xilin; Huang Shengli

2011-01-01

Uranyl ion imprinted polymer beads were prepared by the copolymerization of styrene monomer and divinyl benzene as crosslinking agent in methanol solution,with the UO 2 2+ -o-dihydroxybenzene-4-vinyl pyridine ternary complex as template, the 2, 2'-azo-bis-isobutyronitrile as initiator and UO 2 2+ as the imprinting ion. The uranyl ions were removed from the polymer beads by treating with 6 mol/L HCl, leaving behind cavities that match uranyl ion in size. The treated polymer beads can preconcentrate uranyl ions from dilute aqueous solutions. The adsorption efficiency can reach 99% or above with good selectivity when pH is in the range of 5-7 and the adsorption time is more than 20 min. The elution rate can reach above 99% under the conditions of concentration of HCl being above 1.0 mol/L, elution time more than 20 min and the elution Janume more than 5 times the Janume of ion imprinted polymer. The uranyl ion imprinted polymer beads have been successfully applied to determine micro-uranium in brine samples. The results are satisfactory compared with NBS method.(authors)

Removal of uranyl ions from residual waters using some algae types

International Nuclear Information System (INIS)

Cecal, Al.; Rudic, V.; Gulea, A.; Palamaru, I.; Humelnicu, D.; Salaru, V.V.; Popa, K.

1997-01-01

This paper deals with a study on the bioaccumulation of uranyl ions resulted from residual effluents, by means of some microbiological collectors: Scenedesmus quadricauda, Anabaena karakumica, Calothrix brevissima, Penicillium sp, as well as the Glucide extract of Porphyridium cruentum, in several experimental conditions. The retaining degree of the bioaccumulated uranyl ions, as well as the leaching degree, in HCl and H 2 O media, of the same ions previously retained on algae, were karakumica >Penicillium sp> Calothrix brevissima. The leaching effect of bioaccumulated uranyl ions is higher in hydrochloric acid then in water. (authors)

Enhanced Adsorption and Recovery of Uranyl Ions by NikR Mutant-Displaying Yeast

Directory of Open Access Journals (Sweden)

Kouichi Kuroda

2014-04-01

Full Text Available Uranium is one of the most important metal resources, and the technology for the recovery of uranyl ions (UO22+ from aqueous solutions is required to ensure a semi-permanent supply of uranium. The NikR protein is a Ni2+-dependent transcriptional repressor of the nickel-ion uptake system in Escherichia coli, but its mutant protein (NikRm is able to selectively bind uranyl ions in the interface of the two monomers. In this study, NikRm protein with ability to adsorb uranyl ions was displayed on the cell surface of Saccharomyces cerevisiae. To perform the binding of metal ions in the interface of the two monomers, two metal-binding domains (MBDs of NikRm were tandemly fused via linker peptides and displayed on the yeast cell surface by fusion with the cell wall-anchoring domain of yeast α-agglutinin. The NikRm-MBD-displaying yeast cells with particular linker lengths showed the enhanced adsorption of uranyl ions in comparison to the control strain. By treating cells with citrate buffer (pH 4.3, the uranyl ions adsorbed on the cell surface were recovered. Our results indicate that the adsorption system by yeast cells displaying tandemly fused MBDs of NikRm is effective for simple and concentrated recovery of uranyl ions, as well as adsorption of uranyl ions.

Uptake and speciation of selenium in garlic cultivated in soil amended with symbiotic fungi (mycorrhiza) and selenate

DEFF Research Database (Denmark)

Larsen, Erik Huusfeldt; Lobinski, R.; Burger-Meyer, K.

2006-01-01

The scope of the work was to investigate the influence of selenate fertilisation and the addition of symbiotic fungi (mycorrhiza) to soil on selenium and selenium species concentrations in garlic. The selenium species were extracted from garlic cultivated in experimental plots by proteolytic...... in garlic. The selenium content in garlic, which was analysed by ICP-MS, showed that addition of mycorrhiza to the natural soil increased the selenium uptake by garlic tenfold to 15 mu g g(-1) (dry mass). Fertilisation with selenate and addition of mycorrhiza strongly increased the selenium content...... of soil by mycorrhiza and/or by selenate increased the content of selenium but not the distribution of detected selenium species in garlic. Finally, the use of two-dimensional HPLC (size exclusion followed by reversed-phase) allowed the structural characterisation of gamma...

The gas-phase bis-uranyl nitrate complex ((UO2)2(NO3)5)-: infrared spectrum and structure

International Nuclear Information System (INIS)

Groenewold, G.S.; van Stipdonk, Michael J.; Oomens, Jos; De Jong, Wibe A.; McIlwain, Michael E.

2011-01-01

The infrared spectrum of the bis-uranyl nitrate complex ((UO 2 ) 2 (NO 3 ) 5 ) - was measured in the gas phase using multiple photon dissociation (IRMPD). Intense absorptions corresponding to the nitrate symmetric and asymmetric vibrations, and the uranyl asymmetric vibration were observed. The nitrate v 3 vibrations indicate the presence of nitrate in a bridging configuration bound to both uranyl cations, and probably two distinct pendant nitrates in the complex. The coordination environment of the nitrate ligands and the uranyl cations were compared to those in the mono-uranyl complex. Overall, the uranyl cation is more loosely coordinated in the bis-uranyl complex ((UO 2 ) 2 (NO 3 ) 5 ) - compared to the mono-complex (UO 2 (NO 3 ) 3 ) - , as indicated by a higher O-U-O asymmetric stretching (v 3 ) frequency. However, the pendant nitrate ligands are more strongly bound in the bis-complex than they are in the mono-uranyl complex, as indicated by the v 3 frequencies of the pendant nitrate, which are split into nitrosyl and O-N-O vibrations as a result of bidentate coordination. These phenomena are consistent with lower electron density donation per uranyl by the nitrate bridging two uranyl centers compared to that of a pendant nitrate in the mono-uranyl complex. The lowest energy structure predicted by density functional theory (B3LYP functional) calculations was one in which the two uranyl molecules bridged by a single nitrate coordinated in a bis-bidentate fashion. Each uranyl molecule was coordinated by two pendant nitrate ligands. The corresponding vibrational spectrum was in excellent agreement with the IRMPD measurement, confirming the structural assignment.

The gas-phase bis-uranyl nitrate complex ((UO2)2(NO3)5)-: infrared spectrum and structure

International Nuclear Information System (INIS)

Groenewold, Gary S.; van Stipdonk, Michael J.; Oomens, Jos; de Jong, Wibe; McIlwain, Michael E.

2011-01-01

The infrared spectrum of the bis-uranyl nitrate complex ((UO 2 ) 2 (NO 3 ) 5 ) - was measured in the gas phase using multiple photon dissociation (IRMPD). Intense absorptions corresponding to the nitrate symmetric and asymmetric vibrations, and the uranyl asymmetric vibration were observed. The nitrate nu3 vibrations indicate the presence of nitrate in a bridging configuration bound to both uranyl cations, and probably two distinct pendant nitrates in the complex. The coordination environment of the nitrate ligands and the uranyl cations were compared to those in the mono-uranyl complex. Overall, the uranyl cation is more loosely coordinated in the bis-uranyl complex ((UO 2 ) 2 (NO 3 ) 5 ) - compared to the mono-complex (UO 2 (NO 3 ) 3 ) - , as indicated by a higher O-U-O asymmetric stretching (nu3) frequency. However, the pendant nitrate ligands are more strongly bound in the bis-complex than they are in the mono-uranyl complex, as indicated by the ν 3 frequencies of the pendant nitrate, which are split into nitrosyl and O-N-O vibrations as a result of bidentate coordination. These phenomena are consistent with lower electron density donation per uranyl by the nitrate bridging two uranyl centers compared to that of a pendant nitrate in the mono-uranyl complex. The structure was calculated using density functional theory (B3LYP functional), which produced a structure in which the two uranyl molecules bridged by a single nitrate coordinated in a bis-bidentate fashion. Each uranyl molecule was coordinated by two pendant nitrate ligands. The corresponding vibrational spectrum was in excellent agreement with the IRMPD measurement, confirming the structural assignment.

Variáveis relacionadas à estabilidade de complexos organo-minerais em solos tropicais e subtropicais brasileiros Selected soil-variables related to the stability of organo-minerals complexes in tropical and subtropical brazilian soils

Directory of Open Access Journals (Sweden)

Alberto Vasconcellos Inda Junior

2007-10-01

Full Text Available A estabilidade de complexos organo-minerais é uma característica importante quanto à química e física de solos tropicais e subtropicais. O objetivo deste estudo foi identificar variáveis relacionadas à estabilidade de complexos organo-minerais, avaliada pela energia de ultra-som necessária para a dispersão total do solo em partículas primárias, em seis solos das regiões Sul e Centro-Oeste do Brasil com textura e mineralogia distintas. A energia de ultra-som necessária para dispersão total dos solos variou de 239 a 2.389J mL-1, sendo diretamente relacionada aos teores de carbono orgânico (R²=0,799, PThe stability of organo-mineral complexes is an important characteristic related to the soil chemistry and physics of tropical and subtropical soils. This study was aimed at identifing the variables related to the stability of organo-mineral complexes, evaluated by ultrasonic energy necessary to complete soil dispersion, of six soils from South and West-Center regions of Brazil with distint texture and mineralogy. The ultrasonic energy to complete soil dispersion varied from 239 a 2389J mL-1, and was positively related to the soil organic carbon concentrations (R²=0.799, P<0.05. The clay mineralogy had an important role to the stability of organo-mineral complexes, which were related to the content of low cristalinity iron oxides (R²=0.586, P<0.10, but did not had relationship with the total pedogenic iron oxides. The qualitative analysis of the clay mineralogy, by X-ray diffraction, evidenced that gibbsite and goethite are the main clay minerals related to the stability of organo-mineral complexes, reinforcing the importance of these minerals on the physical protection and coloidal stability of the soil organic matter in the tropical and subtropical soils.

Colorimetric peroxidase mimetic assay for uranyl detection in sea water

KAUST Repository

Zhang, Dingyuan

2015-03-04

Uranyl (UO2 2+) is a form of uranium in aqueous solution that represents the greatest risk to human health because of its bioavailability. Different sensing techniques have been used with very sensitive detection limits especially the recently reported uranyl-specific DNAzymes systems. However, to the best of our knowledge, few efficient detection methods have been reported for uranyl sensing in seawater. Herein, gold nanoclusters (AuNCs) are employed in an efficient spectroscopic method to detect uranyl ion (UO2 2+) with a detection limit of 1.86 ÎM. In the absence of UO2 2+, the BSA-stabilized AuNCs (BSA-AuNCs) showed an intrinsic peroxidase-like activity. In the presence of UO2 2+, this activity can be efficiently restrained. The preliminary quenching mechanism and selectivity of UO2 2+ was also investigated and compared with other ions. This design strategy could be useful in understanding the binding affinity of protein-stabilized AuNCs to UO2 2+ and consequently prompt the recycling of UO2 2+ from seawater.

Orientational order and dynamics of water in bulk and in aqueous solutions of uranyl ions

International Nuclear Information System (INIS)

Chopra, Manish; Choudhury, Niharendu

2014-01-01

Molecular dynamics simulations in canonical ensemble of aqueous solutions of uranyl nitrate and bulk water at ambient condition have been carried out to investigate orientational order and dynamics of water. The orientational distributions of water around a central water molecule in bulk water and around a uranyl ion in an aqueous uranyl solution have been calculated. Orientational dynamics of water in bulk and in aqueous uranyl nitrate solution have also been analysed. (author)

Contribution to the study of uranyl salts in butyl phosphate solutions; Contribution a l'etude des solutions de sels d'uranyle dans les phosphates butyliques

Energy Technology Data Exchange (ETDEWEB)

Coulon, A [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

1965-06-01

A spectroscopic study in the normal infrared region and involving the following associations: tri-alkyl phosphates (tri-butyl, tri-ethyl, tri-methyl), uranyl salts (nitrate, chloride, acetate) has confirmed the existence of an interaction between the phosphoryl group and the uranium atom, as shown by a movement of absorption band for the valency P = 0 from {approx} 1270 cm{sup -1} to {approx} 1180 cm{sup -1}. A study of the preparation, analysis and spectroscopy of the solids obtained by the precipitation of uranyl salts by acid butyl phosphates has been carried out. By infrared spectrophotometry it has been shown that the tri-butyl and di-butyl phosphates are associated in non-polar diluents even before the uranium is introduced. The extraction of uranyl salts from acid aqueous solutions by a diluted mixture of tri-butyl and di-butyl phosphates proceeds by different mechanisms according to the nature of the ion (nitrate or chloride). (author) [French] Une etude spectroscopique dans l'infrarouge moyen portant sur les associations: - phosphates trialcoyliques (tributylique - triethylique - trimethylique) - sels d'uranyle (nitrate, chlorure, acetate) a confirme l'existence d'une interaction entre le groupement phosphoryle et l'atome d'uranium, se manifestant par un deplacement de la bande d'absorption de la vibration de valence P = 0 de {approx} 1270 cm{sup -1} a {approx} 1180 cm{sup -1}. Une etude preparative, analytique et spectroscopique des solides obtenus par precipitation de sels d'uranyle par les phosphates butyliques acides a ete effectuee. La spectrophotomerie infrarouge met en evidence l'association, anterieure a toute introduction d'uranium, des phosphates tributylique et dibutylique dans des diluants non polaires. L'extraction de sels d'uranyle, d'une solution aqueuse acide par un melange dilue de phosphates tributylique et dibutylique, s'effectue suivant des processus differents a la nature de l'anion (nitrate ou chlorure). (auteur)

Chemistry of the uranyl group

International Nuclear Information System (INIS)

Zarli, B.; Dall'olio, G.; Sindellari, L.

1976-01-01

Some uranyl complexes with hexamethylphosphoramide (HMPA) and urea were prepared and characterized. The compounds with the former ligand have the general formula UO 2 X 2 .HMPA (where X = (C 2 H 5 ) 2 NCSe 2 - , (C 2 H 5 ) 2 NCS 2 - or CH 3 COO - ). For the acetato derivatives a dimeric acetato-bridged structure is suggested. Some properties of UO 2 (NO 3 ) 2 .2(HMPA) are also described. With the latter ligand, in addition to the complexes UO 2 (NO 3 ) 2 .2urea and [UO 2 (urea) 4 (H 2 0)](NO 3 ) 2 already known, the novel complexes UO 2 (pycrate) 2 .4urea and [UO 2 (CH 3 COO) 2 .urea]sub(n) (where n is probably 2) have been prepared. All attempts to obtain urea complexes of uranyl diethyldithio- or diethyldiselenocarbamate failed and only adducts of unsatisfactory stoichiometry were isolated. (author)

Chemistry of the uranyl group. VI. Complexes of uranyl with hexamethylphosphoramide and urea

Energy Technology Data Exchange (ETDEWEB)

Zarli, B; Dall' olio, G; Sindellari, L [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi

1976-01-01

Some uranyl complexes with hexamethylphosphoramide (HMPA) and urea were prepared and characterized. The compounds with the former ligand have the general formula UO/sub 2/X/sub 2/.HMPA (where X = (C/sub 2/H/sub 5/)/sub 2/NCSe/sub 2//sup -/, (C/sub 2/H/sub 5/)/sub 2/NCS/sub 2//sup -/ or CH/sub 3/COO/sup -/). For the acetato derivatives a dimeric acetato-bridged structure is suggested. Some properties of UO/sub 2/(NO/sub 3/)/sub 2/.2(HMPA) are also described. With the latter ligand, in addition to the complexes UO/sub 2/(NO/sub 3/)/sub 2/.2urea and (UO/sub 2/(urea)/sub 4/(H/sub 2/0))(NO/sub 3/)/sub 2/ already known, the novel complexes UO/sub 2/(pycrate)/sub 2/.4urea and (UO/sub 2/(CH/sub 3/COO)/sub 2/.urea)sub(n) (where n is probably 2) have been prepared. All attempts to obtain urea complexes of uranyl diethyldithio- or diethyldiselenocarbamate failed and only adducts of unsatisfactory stoichiometry were isolated.

Unusual case of a polar copper(II) uranyl phosphonate that fluoresces

Energy Technology Data Exchange (ETDEWEB)

Nelson, A.G.D.; Albrecht-Schmitt, Th.E. [Department of Civil Engineering and Geological Sciences and Department of Chemistry and Biochemistry, 156 Fitzpatrick Hall, University of Notre Dame, Notre Dame, Indiana (United States)

2010-06-15

A polar Cu(II) uranyl diphosphonate, Cu(H{sub 2}O){sub 4}(UO{sub 2}){sub 3}(H{sub 2}O){sub 2}[CH{sub 2}(PO{sub 3}){sub 2}]{sub 2}.5H{sub 2}O, has been prepared under mild hydrothermal conditions. This compound has direct linkages between the oxo atoms of the uranyl moieties and the Cu(II) centers. Despite the presence of Cu(II) in the structure, vibronically-coupled emission is still observed, most likely because there are two crystallographically unique uranyl moieties, only one of which bonds to Cu(II). (authors)

Mass-spectrometric study of volatile uranyl β-diketonates and their adducts

International Nuclear Information System (INIS)

Adamov, V.M.; Belyaev, B.N.; Berezinskij, S.O.; Sidorenko, G.V.; Suglobov, D.N.

1985-01-01

The mass spectra of a number of uranyl β-diketonates containing methyl, trifluoromethyl and tert-butyl substituents in β-diketonate anion, and their adducts are measured. The form of the unsolvated β-diketonates and their adducts in gas phase is studied. The ways of fragmentation of uranyl β-diketonates and their adducts are investigated. The data concerning the thermal and chemical side reactions proceeding with uranyl β-diketonates and their addicts in an ion source are obtained. The mass spectra of the samples of neptunyl and plutonyl β-diketonate adducts synthesized for the first time are measured

Time-resolved luminescence studies in hydrogen uranyl phosphate intercalated with amines

Energy Technology Data Exchange (ETDEWEB)

Novo, Joao Batista Marques [Departamento de Quimica, Universidade Federal do Parana, CP 19081, 81531-990 Curitiba-PR (Brazil)]. E-mail: jbmnovo@quimica.ufpr.br; Batista, Fabio Roberto [Departamento de Quimica, Universidade Federal do Parana, CP 19081, 81531-990 Curitiba-PR (Brazil); Cunha, Carlos Jorge da [Departamento de Quimica, Universidade Federal do Parana, CP 19081, 81531-990 Curitiba-PR (Brazil); Dias, Lauro Camargo Jr. [Departamento de Quimica, Universidade Federal do Parana, CP 19081, 81531-990 Curitiba-PR (Brazil); Teixeira Pessine, Francisco Benedito [Instituto de Quimica, Universidade Estadual de Campinas, CP 6154, 13084-971 Campinas-SP (Brazil)

2007-05-15

Time-resolved luminescence decays of intercalated compounds of hydrogen uranyl phosphate (HUP) with p-toluidinium (HUPPT), benzylaminium (HUPBZ), {alpha}-methylbenzylaminium (HUPMBZ) and hydroxylaminium (HUPHAM) were studied. The prepared compounds belong to the tetragonal P4/ncc space group and showed 00 l reflections shifted to lower angles relative to HUP, indicating that the intercalation increases the c parameter of the unit cell. The luminescence decays of the compounds with 100% of intercalation ratio (HUPHAM and HUPBZ) were analyzed by Global Analysis, assuming Lianos' stretched exponential as the model function, which can be applied to compounds with restricted geometry and mobile donor and quencher molecules. It was remarkable that the luminescence decays showed that the quenching of the emission of the uranyl ions by the intercalated protonated amines is not restricted by low dimensionality of the host uranyl phosphate, and that a diffusion mechanism occurs. Benzylaminium cation efficiently quenches the excited energy of the uranyl ions at close distance, but the long-range and long-lifetime quenching is hindered. A different situation is found in the case of the small hydroxylaminium cation, where the long distance diffusion of the species is fast, playing an important role in the quenching of the excited uranyl ions at longer times.

Time-resolved luminescence studies in hydrogen uranyl phosphate intercalated with amines

International Nuclear Information System (INIS)

Novo, Joao Batista Marques; Batista, Fabio Roberto; Cunha, Carlos Jorge da; Dias, Lauro Camargo Jr.; Teixeira Pessine, Francisco Benedito

2007-01-01

Time-resolved luminescence decays of intercalated compounds of hydrogen uranyl phosphate (HUP) with p-toluidinium (HUPPT), benzylaminium (HUPBZ), α-methylbenzylaminium (HUPMBZ) and hydroxylaminium (HUPHAM) were studied. The prepared compounds belong to the tetragonal P4/ncc space group and showed 00 l reflections shifted to lower angles relative to HUP, indicating that the intercalation increases the c parameter of the unit cell. The luminescence decays of the compounds with 100% of intercalation ratio (HUPHAM and HUPBZ) were analyzed by Global Analysis, assuming Lianos' stretched exponential as the model function, which can be applied to compounds with restricted geometry and mobile donor and quencher molecules. It was remarkable that the luminescence decays showed that the quenching of the emission of the uranyl ions by the intercalated protonated amines is not restricted by low dimensionality of the host uranyl phosphate, and that a diffusion mechanism occurs. Benzylaminium cation efficiently quenches the excited energy of the uranyl ions at close distance, but the long-range and long-lifetime quenching is hindered. A different situation is found in the case of the small hydroxylaminium cation, where the long distance diffusion of the species is fast, playing an important role in the quenching of the excited uranyl ions at longer times

Investigation into the dehydration of selenate doped Na2M(SO4)2·2H2O (M = Mn, Fe, Co and Ni): Stabilisation of the high Na content alluaudite phases Na3M1.5(SO4)3-1.5x(SeO4)1.5x (M = Mn, Co and Ni) through selenate incorporation

Science.gov (United States)

Driscoll, L. L.; Kendrick, E.; Knight, K. S.; Wright, A. J.; Slater, P. R.

2018-02-01

In this paper we report an investigation into the phases formed on dehydration of Na2M(SO4)2-x(SeO4)x·2H2O (0 ≤ x ≤ 1; M = Mn, Fe, Co and Ni). For the Fe series, all attempts to dehydrate the samples doped with selenate resulted in amorphous products, and it is suspected that a side redox reaction involving the Fe and selenate may be occurring leading to phase decomposition and hence the lack of a crystalline product on dehydration. For M = Mn, Co, Ni, the structure observed was shown to depend upon the transition metal cation and level of selenate doping. An alluaudite phase, Na3M1.5(SO4)3-1.5x(SeO4)1.5x, was observed for the selenate doped compositions, with this phase forming as a single phase for x ≥ 0.5 M = Co, and x = 1.0 M = Ni. For M = Mn, the alluaudite structure is obtained across the series, albeit with small impurities for lower selenate content samples. Although the alluaudite-type phases Na2+2y(Mn/Co)2-y(SO4)3 have recently been reported [1,2], doping with selenate appears to increase the maximum sodium content within the structure. Moreover, the selenate doped Ni based samples reported here are the first examples of a Ni sulfate/selenate containing system exhibiting the alluaudite structure.

Spectroscopic characterization of alkaline earth uranyl carbonates

International Nuclear Information System (INIS)

Amayri, Samer; Reich, Tobias; Arnold, Thuro; Geipel, Gerhard; Bernhard, Gert

2005-01-01

A series of alkaline uranyl carbonates, M[UO 2 (CO 3 ) 3 ].nH 2 O (M=Mg 2 , Ca 2 , Sr 2 , Ba 2 , Na 2 Ca, and CaMg) was synthesized and characterized by inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectrometry (AAS) after nitric acid digestion, X-ray powder diffraction (XRD), and thermal analysis (TGA/DTA). The molecular structure of these compounds was characterized by extended X-ray absorption fine-structure (EXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS). Crystalline Ba 2 [UO 2 (CO 3 ) 3 ].6H 2 O was obtained for the first time. The EXAFS analysis showed that this compound consists of (UO 2 )(CO 3 ) 3 clusters similar to the other alkaline earth uranyl carbonates. The average U-Ba distance is 3.90+/-0.02A.Fluorescence wavelengths and life times were measured using time-resolved laser-induced fluorescence spectroscopy (TRLFS). The U-O bond distances determined by EXAFS, TRLFS, XPS, and Raman spectroscopy agree within the experimental uncertainties. The spectroscopic signatures observed could be useful for identifying uranyl carbonate species adsorbed on mineral surfaces

Influence of nitric acid on the kinetic of complexation of uranyl nitrate extracted by TBP

International Nuclear Information System (INIS)

Pushlenkov, M.F.; Zimenkov, V.V.

1982-02-01

The effect of nitric acid on the solvatation rate of uranyl nitrate with tributyl phosphate is studied. In the process of mass transfer, it is shown that nitric acid enables the extraction of uranyl nitrate, therefore its concentration in the organic phase exceeds that in equilibrium solution. Subsequently uranyl nitrate ''displaces'' nitric acid. The presence of the acid in aqueous and organic phases affects in a complicated manner the rate of solvatation of uranyl nitrate with tributyl phosphate [fr

Subsurface structures in the northern Mare Imbrium measured by Chang'E-3 and SELENE

Science.gov (United States)

Kumamoto, A.; Ishiyama, K.; Feng, J.

2016-12-01

Subsurface structures in the northern Mare Imbrium measured by Chang'E-3 and SELENE have been compared. In Chang'E-3 mission, subsurface radar sounding at (19.51W, 44.12N) was performed by Lunar Penetrating Radar (LPR) onboard the Yutu rover. The LPR was pulse radar operated at two frequencies: 60 MHz and 500 MHz. During its operation period from December 2013 to January 2014, the LPR observed subsurface echoes along the rover's track with total distance of 114 m. From the observation in 60 MHz, the subsurface echoes from buried regolith layers at depths of 35, 50, 140, 240, and 360 m were reported (Xiao et al., 2015). In SELENE mission, global subsurface radar sounding of the moon was performed by Lunar Radar Sounder (LRS) onboard the SELENE (Kaguya) spacecraft from the polar orbit with an altitude of 100 km. The LRS was chirp radar operated in a frequency range from 4-6 MHz. So the range resolution of LRS was 75 m in vacuum. During operation period from December 2007 to September 2008, subsurface echoes from all areas of the Moon was observed with a lateral resolution of 76 m. From the global observation, the subsurface echoes from the buried regolith layers in the neraside maria including Mare Imbrium at depths of several hundred meters were reported (Ono et al., 2009).In the present study, we focus on SELENE/LRS data obtained at (19.50W, 44.12N) which is the nearest to the Chang'E-3 landing site. While clear and large-scale subsurface reflectors, as found in Ono et al. (2009), are not found in it, we can identify some echo components from the depths of 140 ( 2000 ns), 240 ( 4000 ns), and 360 m ( 6000 ns). Further analyses utilizing high-resolution data from Chang'E-3/LPR and large-scale data from SELENE/LRS, we will be able to determine the thickness and large-scale structures of the buried regolith layers found by the both radars, and discuss their formation processes in volcanic history of Mare Imbrium.

Determination of selenite and selenate in human urine by ion chromatography and inductively coupled plasma mass spectrometry

DEFF Research Database (Denmark)

Gammelgaard, Bente; Jons, O.

2000-01-01

The selenium species selenite, selenate and selenomethionine were separated in aqueous solution by ion chromatography. The separation was performed on an IonPac AG11 in series with an AS11 anion exchange column by elution with 25 mM sodium hydroxide in 2% methanol. The Se-78 and Se-82 isotopes were...... monitored in the inductively coupled plasma mass spectrometry (ICP-MS) detector. When the chromatographic system was applied to analysis of urine samples diluted 1 + 1, the selenomethionine signal appeared in the front together with other unresolved selenium species, while the selenite and selenate signals...... and selenate, respectively, corresponding to absolute amounts of 8 and 16 pg, respectively. Calculations were based on peak height measurements of the Se-82 isotope. In 23 analysed urine samples, the concentration of selenite was in the range selenium...

Potential New Ligand Systems for Binding Uranyl Ions in Seawater Environments

Energy Technology Data Exchange (ETDEWEB)

Arnold, John [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

2014-12-13

Work began this quarter on a new project involving a combined computational and biosynthetic approach to selective recognition of uranyl ion in aqueous solution. This project exploits the results of computational studies to discover new ligand classes. Synthetic studies will follow to generate target systems for uranyl binding and determination of binding constants. The process will be iterative, with results from computation informing synthesis, and vice versa. The theme of the ligand classes to be examined initially will be biologically based. New phosphonate-containing α-amino acid N-carboxyanhydride (NCA) monomers were used recently to prepare well-defined phosphonate-containing poly-peptides and block copolypeptides. Our first approach is to utilize these phosphate- and phosphonate-containing NCAs for the coordination of uranyl. The work includes the laboratory-scale preparation of a series of NCAs and the full thermodynamic and spectroscopic characterization of the resulting uranyl complexes. We are also evaluating the sequestering activity in different physiological and environmental conditions of these copolymers as well as their biodegradability.

NATO Advanced Study Institute on Fundamental and Technological Aspects of Organo-f-Element Chemistry

CERN Document Server

Fragalà, Ignazio

1985-01-01

The past decade has seen a dramatic acceleration of activity and interest in phenomena surrounding lanthanide and actinide organo­ metallic compounds. Around the world, active research in organo-f­ element synthesis, chemistry, catalysis, crystallography, and quantum chemistry is in progress. This activity has spanned a remarkably wide range of disciplines, from synthetic/mechanistic inorganic and organic chemistry to radiochemistry, catalytic chemistry, spectroscopy (vibra­ tional, optical, magnetic resonance, photoelectron, Mossbauer), X-ray and neutron diffraction structural analysis, as well as to crystal field and molecular orbital theoretical studies at the interface of chemistry and physics. These investigations have been motivated both by fundamental and applied goals. The evidence that f-element organo­ metallic compounds have unique chemical and physical properties which cannot be duplicated by organometallic compounds of d-block elements has suggested many new areas of endeavor and application....

Novel in situ resistance measurement for the investigation of CIGS growth in a selenization process

International Nuclear Information System (INIS)

Liu Wei; He Qing; Li Fengyan; Li Changjian; Sun Yun; Tian Jianguo; Li Zubin

2009-01-01

During the selenization process of CIGS thin films, the relation between the element loss rate and the precursor depositions are analyzed. The growth of the CIGS thin films during the selenization process is investigated by the novel in situ resistance measurement, by which the formation of compound semiconductors can be observed directly and simultaneously. Their structures, phase evolutions and element losses are analyzed by XRD and XRF. Based on the experimental results, it can be concluded that the phase transforms have nothing to do with the deposition sequences of precursors, while the element loss rates are related to the deposition sequences in this process. In addition, element loss mechanisms of CIGS thin films prepared by the selenization process are analyzed by the phase evolutions and chemical combined path in the In, Ga–Se reaction processes. Moreover it is verified that the element losses are depressed by increasing the ramping-up rate finally. The results provide effective methods to fabricate high-quality CIGS thin films with low element losses

Novel in situ resistance measurement for the investigation of CIGS growth in a selenization process

Science.gov (United States)

Liu, Wei; Tian, Jian-Guo; Li, Zu-Bin; He, Qing; Li, Feng-Yan; Li, Chang-Jian; Sun, Yun

2009-03-01

During the selenization process of CIGS thin films, the relation between the element loss rate and the precursor depositions are analyzed. The growth of the CIGS thin films during the selenization process is investigated by the novel in situ resistance measurement, by which the formation of compound semiconductors can be observed directly and simultaneously. Their structures, phase evolutions and element losses are analyzed by XRD and XRF. Based on the experimental results, it can be concluded that the phase transforms have nothing to do with the deposition sequences of precursors, while the element loss rates are related to the deposition sequences in this process. In addition, element loss mechanisms of CIGS thin films prepared by the selenization process are analyzed by the phase evolutions and chemical combined path in the In, Ga-Se reaction processes. Moreover it is verified that the element losses are depressed by increasing the ramping-up rate finally. The results provide effective methods to fabricate high-quality CIGS thin films with low element losses.

Influence of Acidity on Uranyl Nitrate Association in Aqueous Solutions: A Molecular Dynamics Simulation Study

International Nuclear Information System (INIS)

de Almeida, Valmor F.; Cui, Shengting; Khomami, Bamin; Ye, Xianggui; Smith, Rodney Bryan

2010-01-01

Uranyl ion complexation with water and nitrate is a key aspect of the uranium/plutonium extraction process. We have carried out a molecular dynamics simulation study to investigate this complexation process, including the molecular composition of the various complex species, the corresponding structure, and the equilibrium distribution of the complexes. The observed structures of the complexes suggest that in aqueous solution, uranyls are generally hydrated by 5 water molecules in the equatorial plane. When associating with nitrate ions, a water molecule is replaced by a nitrate ion, preserving the five-fold coordination and planar symmetry. Analysis of the pair correlation function between uranyl and nitrate suggests that nitrates bind to uranyl in aqueous solution mainly in a monodentate mode, although a small portion of bidentates occur. Dynamic association and dissociation between uranyls and nitrates take place in aqueous solution with a substantial amount of fluctuation in the number of various uranyl nitrate species. The average number of the uranyl mononitrate complexes shows a dependence on acid concentration consistent with equilibrium-constant analysis, namely, the concentration of [UO2NO3]+ increases with nitric acid concentration.

Organo-Zintl-based superatoms: [Ge9(CHO)3] and [Ge9(CHO)

Science.gov (United States)

Reddy, G. Naaresh; Jena, Puru; Giri, Santanab

2017-10-01

A systematic study, based on density functional theory and different hybrid functionals for exchange-correlation potential, shows that the electron affinities of organo-zintl clusters [Ge9(R)n] [R = CHO; n = 1, 3] are close to that of chlorine (3.6 eV) and iodine (3.0 eV). A detailed study of the molecular orbitals of these complexes, when compared to those of Al13-, Cl- and I-, confirm that they behave as superatoms, mimicking the chemistry of halogens. This study expands the scope of superatoms by including a new class of pseudo-halogens based on ligated organo-Zintl ions.

Infrared studies on complexes between octaethyltetraamidepyrophosphate (OETAPP) and uranyl salts

International Nuclear Information System (INIS)

Grychowski, P.; Mikulski, J.; Moravets, Ya.; Shara, V.; Shourkova, L.

1981-01-01

Uranyl nitrate and uranyl chloride were extracted from the water phase with CHCl 3 solution of octaethyltetraamidepyrophosphate (OETAPP). Infrared spectra of the organic phases were recorded before and after the extraction. For both systems, the frequency of the P=O stretching mode of OETAPP after the extraction was lowered, which indicates for the formation of OETAPP UO 2 (NO 3 ) 2 and OETAPP UO 2 Cl 2 complexes. If uranyl nitrate was extracted with OETAPP in CCl 4 a precipitate was formed in the solution. From the analysis of the IR spectrum of the precipitate it was concluded that the complex OETAPP UO 2 (NO 3 ) 2 was formed also in this case, however, the complex was insoluble in CCl 4 . (author)

Volatile uranyl hexafluoroacetoacetonate complexes

International Nuclear Information System (INIS)

Dines, M.B.; Hall, R.B.; Kaldor, A.; Kramer, G.M.; Maas, E.T. Jr.

1980-01-01

A composition of matter is described, characterized by the formula UO 2 (CF 3 COCHCOCF 3 ).L where L is a ligand selected from isopropanol, ethanol, isobutanol, tert-butanol, methanol, tetrahydrofuran, acetone, dimethylformamide, n-propanol and ethyl acetate. A process for producing the complex comprises reacting uranyl chloride with a hexafluoroacetylacetonate dissolved in a ligand L: experimental details are given. (U.K.)

Removal of uranyl ions from residual waters using some algae types

International Nuclear Information System (INIS)

Cecal, A.; Palamaru, I.; Humelnicu, D.; Popa, K.; Salaru, V.V.; Rudic, V.; Gulea, A.

1999-01-01

This paper deals with a study on the bioaccumulation of uranyl ions resulted from residual effluents by means of some microbiological collectors: Scenedesmus quadricauda, Anabaena karakumica, Calothrix brevissima, Penicillinium sp, as well as the Glucid extract of Porphyridium cruentum, under various experimental conditions. The retaining degree of the bioaccumulated uranyl ions, as well as the leaching degree, in HCl and H 2 O media, of the same ions previously retained on algae were established. The retaining degree decreases in the series: Scenedesmus quadricauda > Anabaena karakumica > Penicillinium sp > Calothrix brevissima. The leaching effect of bioaccumulated uranyl ions is higher in hydrochloric acid than in water. (author)

Selenate reduction to elemental selenium by anaerobic bacteria in sediments and culture: biogeochemical significance of a novel, sulfate-independent respiration

Science.gov (United States)

Oremland, Ronald S.; Hollibaugh, James T.; Maest, Ann S.; Presser, Theresa S.; Miller, Laurence G.; Culbertson, Charles W.

1989-01-01

Interstitial water profiles of SeO42−, SeO32−, SO42−, and Cl− in anoxic sediments indicated removal of the seleno-oxyanions by a near-surface process unrelated to sulfate reduction. In sediment slurry experiments, a complete reductive removal of SeO42− occurred under anaerobic conditions, was more rapid with H2 or acetate, and was inhibited by O2, NO3−, MnO2, or autoclaving but not by SO42− or FeOOH. Oxidation of acetate in sediments could be coupled to selenate but not to molybdate. Reduction of selenate to elemental selenium was determined to be the mechanism for loss from solution. Selenate reduction was inhibited by tungstate and chromate but not by molybdate. A small quantity of the elemental selenium precipitated into sediments from solution could be resolublized by oxidation with either nitrate or FeOOH, but not with MnO2. A bacterium isolated from estuarine sediments demonstrated selenate-dependent growth on acetate, forming elemental selenium and carbon dioxide as respiratory end products. These results indicate that dissimilatory selenate reduction to elemental selenium is the major sink for selenium oxyanions in anoxic sediments. In addition, they suggest application as a treatment process for removing selenium oxyanions from wastewaters and also offer an explanation for the presence of selenite in oxic waters.

Changes in SeMSC, glucosinolates and sulforaphane levels, and in proteome profile in broccoli (Brassica oleracea var. Italica) fertilized with sodium selenate.

Science.gov (United States)

Sepúlveda, Ignacio; Barrientos, Herna; Mahn, Andrea; Moenne, Alejandra

2013-05-07

The aim of this work was to analyze the effect of sodium selenate fortification on the content of selenomethyl selenocysteine (SeMSC), total glucosinolates and sulforaphane, as well as the changes in protein profile of the inflorescences of broccoli (Brassica oleracea var. Italica). Two experimental groups were considered: plants treated with 100 μmol/L sodium selenate (final concentration in the pot) and control plants treated with water. Fortification began 2 weeks after transplantation and was repeated once a week during 10 weeks. Broccoli florets were harvested when they reached appropriate size. SeMSC content in broccoli florets increased significantly with sodium selenate fortification; but total glucosinolates and sulforaphane content as well as myrosinase activity were not affected. The protein profile of broccoli florets changed due to fortification with sodium selenate. Some proteins involved in general stress-responses were up-regulated, whereas down-regulated proteins were identified as proteins involved in protection against pathogens. This is the first attempt to evaluate the physiological effect of fortification with sodium selenate on broccoli at protein level. The results of this work will contribute to better understanding the metabolic processes related with selenium uptake and accumulation in broccoli.

Changes in SeMSC, Glucosinolates and Sulforaphane Levels, and in Proteome Profile in Broccoli (Brassica oleracea var. Italica Fertilized with Sodium Selenate

Directory of Open Access Journals (Sweden)

Alejandra Moenne

2013-05-01

Full Text Available The aim of this work was to analyze the effect of sodium selenate fortification on the content of selenomethyl selenocysteine (SeMSC, total glucosinolates and sulforaphane, as well as the changes in protein profile of the inflorescences of broccoli (Brassica oleracea var. Italica. Two experimental groups were considered: plants treated with 100 mmol/L sodium selenate (final concentration in the pot and control plants treated with water. Fortification began 2 weeks after transplantation and was repeated once a week during 10 weeks. Broccoli florets were harvested when they reached appropriate size. SeMSC content in broccoli florets increased significantly with sodium selenate fortification; but total glucosinolates and sulforaphane content as well as myrosinase activity were not affected. The protein profile of broccoli florets changed due to fortification with sodium selenate. Some proteins involved in general stress-responses were up-regulated, whereas down-regulated proteins were identified as proteins involved in protection against pathogens. This is the first attempt to evaluate the physiological effect of fortification with sodium selenate on broccoli at protein level. The results of this work will contribute to better understanding the metabolic processes related with selenium uptake and accumulation in broccoli.

Cyanex based uranyl sensitive polymeric membrane electrodes.

Science.gov (United States)

Badr, Ibrahim H A; Zidan, W I; Akl, Z F

2014-01-01

Novel uranyl selective polymeric membrane electrodes were prepared using three different low-cost and commercially available Cyanex extractants namely, bis(2,4,4-trimethylpentyl) phosphinic acid [L1], bis(2,4,4-trimethylpentyl) monothiophosphinic acid [L2] and bis(2,4,4-trimethylpentyl) dithiophosphinic acid [L3]. Optimization and performance characteristics of the developed Cyanex based polymer membrane electrodes were determined. The influence of membrane composition (e.g., amount and type of ionic sites, as well as type of plasticizer) on potentiometric responses of the prepared membrane electrodes was studied. Optimized Cyanex-based membrane electrodes exhibited Nernstian responses for UO₂(2+) ion over wide concentration ranges with fast response times. The optimized membrane electrodes based on L1, L2 and L3 exhibited Nernstian responses towards uranyl ion with slopes of 29.4, 28.0 and 29.3 mV decade(-1), respectively. The optimized membrane electrodes based on L1-L3 showed detection limits of 8.3 × 10(-5), 3.0 × 10(-5) and 3.3 × 10(-6) mol L(-1), respectively. The selectivity studies showed that the optimized membrane electrodes exhibited high selectivity towards UO₂(2+) ion over large number of other cations. Membrane electrodes based on L3 exhibited superior potentiometric response characteristics compared to those based on L1 and L2 (e.g., widest linear range and lowest detection limit). The analytical utility of uranyl membrane electrodes formulated with Cyanex extractant L3 was demonstrated by the analysis of uranyl ion in different real samples for nuclear safeguards verification purposes. The results obtained using direct potentiometry and flow-injection methods were compared with those measured using the standard UV-visible and inductively coupled plasma spectroscopic methods. © 2013 Published by Elsevier B.V.

Electron spectra and mechanism of complexing of uranyl nitrate in water-acetone solutions

International Nuclear Information System (INIS)

Zazhogin, A.A.; Zazhogin, A.P.; Komyak, A.I.; Serafimovich, A.I.

2003-01-01

Based on the analysis of the luminescence and electronic absorption spectra, the processes of complexing in an aqueous solution of UO 2 (NO 3 ) 2 ·6H 2 O with small additions of acetone have been studied. In a pure aqueous solution, uranyl exists as the complex UO 2 ·5H 2 O. It is shown that the addition of acetone to the solution leads to the displacement of some water molecules out of the first coordination sphere of uranyl and the formation of the uranyl nitrate dihydrate complexes UO 2 (NO 3 ) 2 ·2H 2 O. It has been established that the stability of these complexes is determined by the decrease in the water activity and in the degree of hydration of uranyl and nitrate, which is the result of the local increase in the concentration of acetone molecules (due to their hydrophobicity) in the regions of the solution where uranyl and nitrate ions are found. The experimental facts supported the mechanism proposed are presented. (authors)

A study of precipitation from pure solutions of uranyl nitrate

International Nuclear Information System (INIS)

Decrop, J.; Holder, J.; Sauteron, J.

1961-01-01

After its purification by extraction of the uranyl nitrate from the organic solvent, uranium has to be converted into solid form again: uranium trioxide (UO 3 ). It can be done either by thermal decomposition of uranyl nitrate or by precipitation of uranium, followed by filtration and calcination. Only the second method has been studied for now at the Bouchet plant. This paper reports the bench-scale and pilot-scale experiments of the studies of the precipitation of pure solutions of uranyl nitrate using ammonia (gaseous or in solution) or ammonium carbonate. These have been carried out at the Bouchet plant. It investigates the chemical aspect (pH, precipitates chemical composition) and the technical aspect of the different ways of precipitation (conditions of precipitation, decantation and filtration of precipitates). (M.P.)

Preparation of working calibration and test materials: uranyl nitrate solution

International Nuclear Information System (INIS)

Yamamura, S.S.; Spraktes, F.W.; Baldwin, J.M.; Hand, R.L.; Lash, R.P.

1977-05-01

Reliable working calibration and test materials (WCTMs) are essential to a meaningful analytical measurements quality assurance program. This report describes recommended methods for the preparation of uranyl nitrate solution WCTMs for testing analytical methods, for calibrating methods, and for testing personnel. Uranyl nitrate solution WCTMs can be synthesized from characterized starting materials or prepared from typical plant materials by thorough characterization with reference to primary or secondary reference calibration and test materials (PRCTMs or SRCTMs). Recommended starting materials are described along with detailed procedures for (a) preparing several widely-used types of uranyl nitrate solution WCTMs, (b) packaging the WCTMs, (c) analyzing the WCTMs to establish the reference values or to confirm the synthesis, and (d) statistically evaluating the analytical data to assign reference values and to assess the accuracy of the WCTMs

New chemistry of the uranyl ion in non aqueous media

International Nuclear Information System (INIS)

Siffredi, G.

2008-12-01

This work deals with new aspects of the chemistry of the uranyl(VI) ion {UO 2 } 2+ in anhydrous polar organic solvents such as the activation of the reputedly inert U-O yl bond and the controlled reduction of this species which represent a particularly active field of research that attracts much attention for both its fundamental aspects and applications. Treatment of uranyl(VI) compounds UO 2 X' 2 (X' = I, OTf, Cl) with Me 3 SiX (X = Cl, Br, I) reagents, in various anhydrous polar organic solvents, has been first considered. In most cases, reduction into tetravalent species with complete de-oxygenation of the uranyl {UO 2 } 2+ ion is observed. The reaction is particularly efficient in acetonitrile where the tetravalent [UX 4 (MeCN) 4 ] complexes, which are useful precursors in uranium chemistry, are isolated. In the course of these reactions, the influence of the solvent, the nature of X' and X in the UO 2 X' 2 precursor and the Me 3 SiX reagent are pointed out. Reaction of the uranyl(VI) UO 2 X 2 (X = I, Cl, OTf, NO 3 ) precursors with the anionic MC 5 R 5 (M = K, R = H, Me; M= Li, R = Me; M= Tl, R = H) reagents did not lead to the organometallic [(η 5 -C 5 R 5 ) n UO 2 X 2-n ] species (n = 1, 2) but to pentavalent uranyl(V) complexes. This method is a facile and rapid route towards the formation of stable pentavalent uranyl which offers promising sources for further U(V) chemical developments and for fundamental and applied interests. Their structure is strongly dependent on the nature of the solvent, the additional ligands X and of the M + cation. In pyridine, the {UO 2 (py) 5 } + ion appears to be an ubiquitous and a quite stable entity. The coordinating properties of the basic oxo groups, which coordinate easily to M + ions (M= Li, K, Tl), favour structural diversity with formation of hetero-polymetallic complexes such as [{UO 2 (py) 5 }{MX(py) 2 }] (M= Li, X I), [{UO 2 (py) 5 }{MX 2 (py) 2 }] ∞ (M= K, Tl, X= OTf; M= K, X= I), [{UO 2 (py) 5 }(M 2 X 3 )]�

Surface complexation modeling of uranyl adsorption on corrensite from the Waste Isolation Pilot Plant Site

Energy Technology Data Exchange (ETDEWEB)

Park, Sang-Won; Leckie, J.O. [Stanford Univ., CA (United States); Siegel, M.D. [Sandia National Labs., Albuquerque, NM (United States)

1995-09-01

Corrensite is the dominant clay mineral in the Culebra Dolomite at the Waste Isolation Pilot Plant. The surface characteristics of corrensite, a mixed chlorite/smectite clay mineral, have been studied. Zeta potential measurements and titration experiments suggest that the corrensite surface contains a mixture of permanent charge sites on the basal plane and SiOH and AlOH sites with a net pH-dependent charge at the edge of the clay platelets. Triple-layer model parameters were determined by the double extrapolation technique for use in chemical speciation calculations of adsorption reactions using the computer program HYDRAQL. Batch adsorption studies showed that corrensite is an effective adsorbent for uranyl. The pH-dependent adsorption behavior indicates that adsorption occurs at the edge sites. Adsorption studies were also conducted in the presence of competing cations and complexing ligands. The cations did not affect uranyl adsorption in the range studied. This observation lends support to the hypothesis that uranyl adsorption occurs at the edge sites. Uranyl adsorption was significantly hindered by carbonate. It is proposed that the formation of carbonate uranyl complexes inhibits uranyl adsorption and that only the carbonate-free species adsorb to the corrensite surface. The presence of the organic complexing agents EDTA and oxine also inhibits uranyl sorption.

Surface complexation modeling of uranyl adsorption on corrensite from the Waste Isolation Pilot Plant Site

International Nuclear Information System (INIS)

Park, Sang-Won; Leckie, J.O.; Siegel, M.D.

1995-09-01

Corrensite is the dominant clay mineral in the Culebra Dolomite at the Waste Isolation Pilot Plant. The surface characteristics of corrensite, a mixed chlorite/smectite clay mineral, have been studied. Zeta potential measurements and titration experiments suggest that the corrensite surface contains a mixture of permanent charge sites on the basal plane and SiOH and AlOH sites with a net pH-dependent charge at the edge of the clay platelets. Triple-layer model parameters were determined by the double extrapolation technique for use in chemical speciation calculations of adsorption reactions using the computer program HYDRAQL. Batch adsorption studies showed that corrensite is an effective adsorbent for uranyl. The pH-dependent adsorption behavior indicates that adsorption occurs at the edge sites. Adsorption studies were also conducted in the presence of competing cations and complexing ligands. The cations did not affect uranyl adsorption in the range studied. This observation lends support to the hypothesis that uranyl adsorption occurs at the edge sites. Uranyl adsorption was significantly hindered by carbonate. It is proposed that the formation of carbonate uranyl complexes inhibits uranyl adsorption and that only the carbonate-free species adsorb to the corrensite surface. The presence of the organic complexing agents EDTA and oxine also inhibits uranyl sorption

Study of the Cupriavidus metallidurans CH34 resistance of selenite and selenate oxy-anions: accumulation, localisation and transformation of selenium

International Nuclear Information System (INIS)

Avoscan, L.

2007-06-01

Selenium is an essential trace element for the living organisms but it is very toxic at high concentration. Selenite and selenate oxides, soluble forms, highly toxic and bio-assimilable, are the most prevalent forms in the environment. Some soil micro-organisms play a dominant role and contribute to the natural cycle of selenium. Our study model, Cupriavidus (formerly Ralstonia) metallidurans CH34, a telluric bacterium characteristic of metal-contaminated biotopes, is known to resist selenite by reducing it into elemental selenium, an insoluble and less toxic form of selenium. In order to better understand the mechanisms of selenium reduction in the bacteria, three methods of speciation were combined (XAS (XANES and EXAFS), HPLC-ICP-MS and SDS-PAGEPIXE). They were completed by the direct quantification of selenium accumulated in the bacteria. Speciation analyses highlighted the existence of two mechanisms of reduction of selenium oxides in C. metallidurans CH34. Assimilation transforms selenite and selenate into organic selenium, identified as seleno-methionine and leads to its non-specific incorporation into bacterial proteins (presence of selenious proteins). Detoxication precipitates selenite in nano-particles of elemental selenium. This way of detoxication is not set up after an exposure to selenate although it is nevertheless possible to detect elemental selenium but in very small amount compared to the exposure of selenite. Seleno-diglutathion is detected in bacteria stressed by an exposure to selenate in medium limited in sulphate. Bacteria exposed to selenite accumulate 25 times more selenium than when they are exposed to selenate. The study of mutants resistant to selenite, which do not express the membrane protein DedA, showed that the accumulation of selenium after exposure to selenite is decreased compared with the wild strain meaning probable link between the transport of selenite and the DedA protein. Finally, selenate would use the sulphate permease

Magnetic biosorbent for removal of uranyl ions

International Nuclear Information System (INIS)

Yamamura, Amanda P.G.; Yamaura, Mitiko; Costa, Caroline H.

2009-01-01

In this work magnetic biosorbent, which consisted of sugarcane bagasse as polymeric matrix with magnetite nanoparticles, was prepared. This magnetic composite has the purpose to remove uranyl ions from aqueous effluents. The magnetite was synthetized by simultaneous precipitation by addition a solution of NaOH to the aqueous solution containing Fe2+ and Fe3+. This magnetic bagasse biosorbent have presented superparamagnetic properties, that is, it have showed a high magnetization of saturation without hysteresis. The magnetic biosorbent was utilized to remove uranyl ions from water. Radioactive uranium waste is generated in hospitals, universities and it is used as fuel for nuclear power plants. Variables of adsorption process of uranyl ions by magnetic biosorbent in nitric solutions were investigated, such as, time required for the uranium-magnetic bagasse biosorbent equilibrium in the interval from 20 to 90 min, pH in the intervals from 2 to 5 and 10, stirring speed from 240 to 500 r.p.m. and biosorbent dose from 2 to 25 g.L-1 were investigated. Equilibrium isotherm was verified according to the Langmuir and Freundlich adsorption isotherm models. The highest adsorption capacity reached 17 mg.g-1. The Gibbs free energy indicated to be spontaneous adsorption. This work updates the paper was presented on the 2007 INAC.

DNA conformational analysis in solution by uranyl mediated photocleavage

DEFF Research Database (Denmark)

Nielsen, Peter E.; Møllegaard, N E; Jeppesen, C

1990-01-01

Uranyl mediated photocleavage of double stranded DNA is proposed as a general probing for DNA helix conformation in terms of minor groove width/electronegative potential. Specifically, it is found that A/T-tracts known to constitute strong distamycin binding sites are preferentially photocleaved ......, uranyl photocleavage of the internal control region (ICR) of the 5S-RNA gene yields a cleavage modulation pattern fully compatible with that obtained by DNase I which also--in a more complex way--senses DNA minor groove width....

Thermodynamics of Uranyl Minerals: Enthalpies of Formation of Uranyl Oxide Hydrates

International Nuclear Information System (INIS)

Kubatko, K.; Helean, K.; Navrotsky, A.; Burns, P.C.

2005-01-01

The enthalpies of formation of seven uranyl oxide hydrate phases and one uranate have been determined using high-temperature oxide melt solution calorimetry: [(UO 2 ) 4 O(OH) 6 ](H 2 O) 5 , metaschoepite; β-UO 2 (OH) 2 ; CaUO 4 ; Ca(UO 2 ) 6 O 4 (OH) 6 (H 2 O) 8 , becquerelite; Ca(UO 2 ) 4 O 3 (OH) 4 (H 2 O) 2 ; Na(UO 2 )O(OH), clarkeite; Na 2 (UO 2 ) 6 O 4 (OH) 6 (H 2 O) 7 , the sodium analogue of compreignacite and Pb 3 (UO 2 ) 8 O 8 (OH) 6 (H 2 O) 2 , curite. The enthalpy of formation from the binary oxides, ΔH f-ox , at 298 K was calculated for each compound from the respective drop solution enthalpy, ΔH ds . The standard enthalpies of formation from the elements, ΔH f o , at 298 K are -1791.0 ± 3.2, -1536.2 ± 2.8, -2002.0 ± 3.2, -11389.2 ± 13.5, -6653.1 ± 13.8, -1724.7 ± 5.1, -10936.4 ± 14.5 and -13163.2 ± 34.4 kJ mol -1 , respectively. These values are useful in exploring the stability of uranyl oxide hydrates in auxiliary chemical systems, such as those expected in U-contaminated environments

Molecular approach of uranyl/mineral surfaces: theoretical approach

International Nuclear Information System (INIS)

Roques, J.

2009-01-01

As migration of radio-toxic elements through the geosphere is one of the processes which may affect the safety of a radioactive waste storage site, the author shows that numerical modelling is a support to experimental result exploitation, and allows the development of new interpretation and prediction codes. He shows that molecular modelling can be used to study processes of interaction between an actinide ion (notably a uranyl ion) and a mineral surface (a TiO 2 substrate). He also reports the predictive theoretical study of the interaction between an uranyl ion and a gibbsite substrate

Uranyl peroxide enhanced nuclear fuel corrosion in seawater.

Science.gov (United States)

Armstrong, Christopher R; Nyman, May; Shvareva, Tatiana; Sigmon, Ginger E; Burns, Peter C; Navrotsky, Alexandra

2012-02-07

The Fukushima-Daiichi nuclear accident brought together compromised irradiated fuel and large amounts of seawater in a high radiation field. Based on newly acquired thermochemical data for a series of uranyl peroxide compounds containing charge-balancing alkali cations, here we show that nanoscale cage clusters containing as many as 60 uranyl ions, bonded through peroxide and hydroxide bridges, are likely to form in solution or as precipitates under such conditions. These species will enhance the corrosion of the damaged fuel and, being thermodynamically stable and kinetically persistent in the absence of peroxide, they can potentially transport uranium over long distances.

Influence of uranyl dibutylphosphate on the UV/VIS spectrophotometric online monitoring of uranium in tributylphosphate/hydrocarbon solvent

International Nuclear Information System (INIS)

Creech, E.T.; Rutenberg, A.C.; Smithwick, R.W.; Seals, R.D.

1984-01-01

In the uranium recovery process at the Y-12 Plant uranium is recovered from aqueous uranyl solutions by extraction into a solvent consisting of 30% tributylphosphate (TBP) and 70% hydrocarbon solvent. Within this process the uranium is continuously monitored by a UV/VIS absorbance measurement of the uranyl/tributylphosphate complex in the organic phase. The uranium is then further extracted from the organic phase to a final water phase. Dibutylphosphate (DBP), which is a decomposition product of TBP, builds up in the organic solvent. A very strong complex of uranyl/dibutylphosphate is formed which cannot be extracted into the aqueous phase. Prior to this work the uranyl/dibutylphosphate complex absorbance was assumed to be the same as the uranyl tributylphosphate complex. To determine the effect of the presence of uranyl/dibutylphosphate on the continuous UV/VIS monitor required (a) the purification of commercial dibutylphosphate, (b) the synthesis, and (c) the characterization of uranyl/dibutylphosphate

Contribution of SELENE-2 geodetic measurements to constrain the lunar internal structure

Science.gov (United States)

Matsumoto, K.; Kikuchi, F.; Yamada, R.; Iwata, T.; Kono, Y.; Tsuruta, S.; Hanada, H.; Goossens, S. J.; Ishihara, Y.; Kamata, S.; Sasaki, S.

2012-12-01

Internal structure and composition of the Moon provide important clue and constraints on theories for how the Moon formed and evolved. The Apollo seismic network has contributed to the internal structure modeling. Efforts have been made to detect the lunar core from the noisy Apollo data (e.g., [1], [2]), but there is scant information about the structure below the deepest moonquakes at about 1000 km depth. On the other hand, there have been geodetic studies to infer the deep structure of the Moon. For example, LLR (Lunar Laser Ranging) data analyses detected a displacement of the lunar pole of rotation, indicating that dissipation is acting on the rotation arising from a fluid core [3]. Bayesian inversion using geodetic data (such as mass, moments of inertia, tidal Love numbers k2 and h2, and quality factor Q) also suggests a fluid core and partial melt in the lower mantle region [4]. Further improvements in determining the second-degree gravity coefficients (which will lead to better estimates of moments of inertia) and the Love number k2 will help us to better constrain the lunar internal structure. Differential VLBI (Very Long Baseline Interferometry) technique, which was used in the Japanese lunar exploration mission SELENE (Sept. 2007 - June 2009), is expected to contribute to better determining the second-degree potential Love number k2 and low-degree gravity coefficients. SELENE will be followed by the future lunar mission SELENE-2 which will carry both a lander and an orbiter. We propose to put the SELENE-type radio sources on these spacecraft in order to accurately estimate k2 and the low-degree gravity coefficients. By using the same-beam VLBI tracking technique, these parameters will be retrieved through precision orbit determination of the orbiter with respect to the lander which serves as a reference. The VLBI mission with the radio sources is currently one of the mission candidates for SELENE-2. We have conducted a preliminary simulation study on the

Separation of selenium compounds by CE-ICP-MS in dynamically coated capillaries applied to selenized yeast samples

DEFF Research Database (Denmark)

Bendahl, Lars; Gammelgaard, Bente

2004-01-01

The selenium species in nutritional supplement tablets, based on selenized yeast, were separated by capillary zone electrophoresis using capillaries coated dynamically with poly(vinyl sulfonate) and detected by ICP-MS. Sample pre-treatment consisted of cold-water extraction by sonication and subs......The selenium species in nutritional supplement tablets, based on selenized yeast, were separated by capillary zone electrophoresis using capillaries coated dynamically with poly(vinyl sulfonate) and detected by ICP-MS. Sample pre-treatment consisted of cold-water extraction by sonication...

Separation of uranyl ion using polyaniline

International Nuclear Information System (INIS)

Jayshree Ramkumar; Chandramouleeswaran, S.

2013-01-01

Polyaniline (Pani) was synthesized by the chemical oxidation of aniline. The use of persulphate instead of dichromate was desired in order to avoid the incorporation of chromium in the polymer matrix. The presence of chromium in the matrix, when dichromate was used as an oxidant, was confirmed by various techniques. The batch mode experiments showed that Pani could be used for separation of different metal ions. These ions were converted into their anionic complexes using suitable complexing agents. It was found that EDTA was used as a suitable reagent for the separation of Cu 2+ from Zn 2+ whereas the uranyl ion uptake could be increased to about 95 % when carbonate was used instead of EDTA as complexing agent. A possible application of the above exchange system to preconcentration of uranyl ion from seawater has also been examined. (author)

Spectroscopic studies of 2-thenoyltrifluoro acetonate of uranyl salts doped with europium

International Nuclear Information System (INIS)

Nakagawa, F.T.; Luiz, J.E.M. de Sa; Felinto, M.C.F.C.; Brito, H.F.; Teotonio, E.E.S.

2006-01-01

Uranyl compounds present a great potential as luminescence materials. Some examples of applications are: in laser technology, cathode ray tube, X-rays diagnostic. In this work it was studied the synthesis, characterization and spectroscopic properties study of uranyl 2-thenoyl trifluoroacetonate and uranyl 2- thenoyl trifluoroacetonate doped with europium. The compounds were synthesized and characterized by infrared absorption spectroscopy, thermal analysis, scanning electronic microscopy, and electronic spectroscopy of emission and excitation. The Eu 3+ ion acted as an effective luminescent probe, however the process of energy transfer from UO 2 2+ to Eu 3+ ion has not been efficient. (author)

Radiolysis studies of uranyl nitrate solution in nitric acid medium

International Nuclear Information System (INIS)

Siri, Sandra; Mondino, Angel V.

2005-01-01

The radiolysis of acidic uranyl nitrate solutions was investigated using Co-60 gamma radiation. Hydrogen peroxide was determined as a function of increasing dose. The UV-vis absorption spectra of the irradiated solutions were measured and the spectral changes were analyzed. The increasing dose increases the absorbance intensities, possibly by an increment in nitrate concentration produced by radiolysis, which can originate the formation of different uranyl complexes in solution. (author)

Decomposition of uranyl peroxo-carbonato complex ion in the presence of metal oxides in carbonate media

International Nuclear Information System (INIS)

Dong-Yong Chung; Min-Sung Park; Keun-Young Lee; Eil-Hee Lee; Kwang-Wook Kim; Jei-Kwon Moon

2015-01-01

Uranium oxide was dissolved in the form of the uranyl peroxo-carbonato complex ion, UO 2 (O 2 )(CO 3 ) 2 4- in carbonate solutions with hydrogen peroxide. When UO 2 (O 2 )(CO 3 ) 2 4- ions lose their peroxide component, they become a stable species of uranyl tricarbonato complex ion, UO 2 (O 2 )(CO 3 ) 2 4- . The uranyl peroxo-carbonato complex self-decomposed more rapidly into the uranyl tricarbonato complex ion in the presence of a metal oxide in the carbonate solution. In this study, decomposition of the uranyl peroxo-carbonato complex in a carbonate solution was investigated in the presence of several metal oxides using absorption spectroscopy. (author)

Quantification of uranyl in presence of citric acid; Cuantificacion de uranilo en presencia de acido citrico

Energy Technology Data Exchange (ETDEWEB)

Garcia G, N.; Barrera D, C.E. [UAEM, Facultad de Quimica, 50000 Toluca, Estado de Mexico (Mexico); Ordonez R, E. [ININ, 52750 La Marquesa, Estado de Mexico (Mexico)]. e-mail: nidgg@yahoo.com.mx

2007-07-01

To determine the influence that has the organic matter of the soil on the uranyl sorption on some solids is necessary to have a detection technique and quantification of uranyl that it is reliable and sufficiently quick in the obtaining of results. For that in this work, it intends to carry out the uranyl quantification in presence of citric acid modifying the Fluorescence induced by UV-Vis radiation technique. Since the uranyl ion is very sensitive to the medium that contains it, (speciation, pH, ionic forces, etc.) it was necessary to develop an analysis technique that stands out the fluorescence of uranyl ion avoiding the out one that produce the organic acids. (Author)

Sorption rate of uranyl ions by hyphan cellulose exchangers and by hydrated titanium dioxide

International Nuclear Information System (INIS)

Ambe, F.; Burba, P.; Lieser, K.H.

1979-01-01

Sorption of uranyl ions by the cellulose exchanger Hyphan proceeds rather fast. Two steps are observed with half-times of the order of 10 s and 2 min. The majority of the uranyl ions is bound in 1 min. Sorption of uranyl ions by titanium dioxide is a very slow process. For particle sizes between 0,1 and 0,5 mm the half-time is about 3 h and equilibrium is attained in about 1 day. The effect of stirring suspensions of inorganic sorbents like titanium dioxide in solution is investigated in detail. Sorption of uranyl ions by titanium dioxide and change in pH in solution are measured simultaneously as a function of time. (orig.) [de

Uranium (VI) chemistry at the interface solution/minerals (quartz and aluminium hydroxide): experiments and spectroscopic investigations of the uranyl surface species

International Nuclear Information System (INIS)

Froideval, A.

2004-09-01

This study deals with the understanding of the uranyl chemistry at the 0.1 M NaNO 3 solution/mineral (quartz and aluminium hydroxide) interface. The aims are:(i) to identify and to characterize the different uranyl surface species (mononuclear, polynuclear complexes and/or precipitates...), i.e. the coordination environments of sorbed/precipitated uranyl ions, by using X-ray photoelectron spectroscopy (XPS), extended X-ray absorption fine structure (EXAFS) and time-resolved laser-induced fluorescence spectroscopy (TRLFS), and;(ii) to investigate the influence of pH, initial uranyl aqueous concentration and hydroxyl ligand concentration on the uranyl surface speciation. Our study on the speciation of uranyl ions at the quartz surface (i) confirms the formation of uranyl polynuclear/oligomers on quartz from moderate (1 μmol/m 2 ) to high (26 μmol/m 2 ) uranyl surface concentrations and (ii) show that theses polynuclear species coexist with uranyl mononuclear surface species over a pH range ≅ 5-8.5 and a wide range of initial uranyl concentration o f the solutions (10-100 μM). The uranyl concentration of these surface species depends on pH and on the initial uranyl aqueous concentration. Hydrate (surface-) precipitates and/or adsorbed polynuclear species and monomeric uranyl surface complexes are formed on aluminium hydroxide. Uranyl mononuclear complexes are predominant at acidic pH, as well as uranyl in solution or on the surface. Besides mononuclear species, precipitates and/or adsorbed polynuclear species are predominantly formed at neutral pH values on aluminium hydroxide. A main contribution of our investigations is that precipitation and/or adsorption of polynuclear species seem to occur at low uranyl surface concentrations (0.01-0.4 μmol/m 2 ). The uranyl surface speciation is mainly dependent on the pH and the aluminol ligand concentration. (author)

A Comprehensive Study of One-Step Selenization Process for Cu(In1-x Ga x )Se2 Thin Film Solar Cells.

Science.gov (United States)

Chen, Shih-Chen; Wang, Sheng-Wen; Kuo, Shou-Yi; Juang, Jenh-Yih; Lee, Po-Tsung; Luo, Chih Wei; Wu, Kaung-Hsiung; Kuo, Hao-Chung

2017-12-01

In this work, aiming at developing a rapid and environmental-friendly process for fabricating CuIn 1-x Ga x Se 2 (CIGS) solar cells, we demonstrated the one-step selenization process by using selenium vapor as the atmospheric gas instead of the commonly used H 2 Se gas. The photoluminescence (PL) characteristics indicate that there exists an optimal location with superior crystalline quality in the CIGS thin films obtained by one-step selenization. The energy dispersive spectroscopy (EDS) reveals that the Ga lateral distribution in the one-step selenized CIGS thin film is intimately correlated to the blue-shifted PL spectra. The surface morphologies examined by scanning electron microscope (SEM) further suggested that voids and binary phase commonly existing in CIGS films could be successfully eliminated by the present one-step selenization process. The agglomeration phenomenon attributable to the formation of MoSe 2 layer was also observed. Due to the significant microstructural improvement, the current-voltage (J-V) characteristics and external quantum efficiency (EQE) of the devices made of the present CIGS films have exhibited the remarkable carrier transportation characteristics and photon utilization at the optimal location, resulting in a high conversion efficiency of 11.28%. Correlations between the defect states and device performance of the one-step selenized CIGS thin film were convincingly delineated by femtosecond pump-probe spectroscopy.

Time-resolved luminescence spectroscopy of trace uranyl in wet sand

International Nuclear Information System (INIS)

Freed, D.

1993-01-01

The objective of the project was to develop a technique to observe and characterize the behaviour of uranium in unsaturated groundwater flow systems, particularly with regard to unstable ''fingered'' flow, which could drastically reduce time of travel. The actual experimental work described was a study of the feasibility of detecting uranyl at the parts-per-billion level in aqueous solution by means of its luminescence spectrum. A high-power UV laser was used to excite aqueous uranyl in a wet sand mixture; the characteristic green phosphorescence emitted in the decay transition was detected by a photomultiplier tube; and the amplified signal was sent to an oscilloscope in communication with Macintosh data acquisition software. At the time of the conference, a more sophisticated sample configuration for imaging the flow of uranyl was already under development. 5 refs., 3 figs

Time-resolved luminescence spectroscopy of trace uranyl in wet sand

Energy Technology Data Exchange (ETDEWEB)

Freed, D [Massachusetts Inst. of Tech., Cambridge, MA (United States)

1994-12-31

The objective of the project was to develop a technique to observe and characterize the behaviour of uranium in unsaturated groundwater flow systems, particularly with regard to unstable ``fingered`` flow, which could drastically reduce time of travel. The actual experimental work described was a study of the feasibility of detecting uranyl at the parts-per-billion level in aqueous solution by means of its luminescence spectrum. A high-power UV laser was used to excite aqueous uranyl in a wet sand mixture; the characteristic green phosphorescence emitted in the decay transition was detected by a photomultiplier tube; and the amplified signal was sent to an oscilloscope in communication with Macintosh data acquisition software. At the time of the conference, a more sophisticated sample configuration for imaging the flow of uranyl was already under development. 5 refs., 3 figs.

1H chemically induced dynamic nuclear polarization in the photodecomposition of uranyl carboxylates

International Nuclear Information System (INIS)

Rykov, S.V.; Khudyakov, I.V.; Skakovsky, E.D.; Burrows, H.D.; Formosinho, S.J.; Miguel, M. da G.M.

1991-01-01

Chemically induced dynamic nuclear polarization ( 1 H CIDNP) has been observed during photolysis of uranyl salts of pivalic, propionic, and acetic acids in D 2 O solution, [ 2 H 6 ]acetone, [ 2 H 4 ]methanol, or in some other solvent. The multiplet polarization of isobutene and isobutane protons has been found under photolysis of deoxygenated pivalate solution. The polarized compounds are formed in the triplet pairs of tert-butyl free radicals. 1 H Emission of the tert-butylperoxyl group and emission of 1 H from isobutene have been recorded under photolysis of air-saturated pivalate solutions. The CIDNP of butane protons stays as a multiplet. Such changes in the presence of air/oxygen have arisen apparently because of the formation of tert-butylperoxyl free radical and its reaction with tert-butyl radical products, i.e. hydroperoxide (peroxide) and isobutene. Isobutene probably forms a complex with molecular oxygen which has a very short proton relaxation time. During the photolysis of uranyl pivalate in the presence of p-benzoquinone (5 x 10 -2 -0.1 mol dm -3 ) we have not observed any CIDNP, whereas under p-benzoquinone concentrations of 10 -3 -10 -2 mol dm -3 the CIDNP from both hydroquinone and p-benzoquinone has been followed. Photolysis of uranyl propionate has led to CIDNP from butane protons. An emission from methyl group protons of a compound with an ethylperoxyl fragment in the presence of air/oxygen has been observed. The same polarization picture has arisen under interaction of photoexcited uranyl with propionic acid. During the photolysis of uranyl acetate at relatively low concentrations (10 -2 mol dm -3 ) a CIDNP very similar to that registered for uranyl propionate was recorded. The ethyl fragment is probably obtained in reactions for two methyl radicals formed from acetate with the parent uranyl acetate, namely hydrogen-atom abstraction and addition reactions. (author)

Thermodynamics of dehydration process of uranyl nitrate pentahydrate of thorium

International Nuclear Information System (INIS)

Khamidov, F.A.; Mirsaidov, I.U.; Nazarov, K.M.; Nasriddinov, S.K.; Badalov, A.B.

2010-01-01

Present article is devoted to thermodynamics of dehydration process of uranyl nitrate pentahydrate of thorium. The results of researches of dehydration process of uranyl nitrate pentahydrate of thorium Th(NO_3)_4·5H_2O were considered. The researches were carried out by means of tensimeter method with membrane zero-manometer under equilibrium conditions and at 300-450 K temperature ranges. The thermodynamic characteristics of dehydration process of initial crystalline hydrate was defined.

A surface structural model for ferrihydrite II: Adsorption of uranyl and carbonate

NARCIS (Netherlands)

Hiemstra, T.; Riemsdijk, van W.H.; Rossberg, A.; Ulrich, K.

2009-01-01

The adsorption of uranyl (UO22+) on ferrihydrite has been evaluated with the charge distribution (CD) model for systems covering a very large range of conditions, i.e. pH, ionic strength, CO2 pressure, U(VI) concentration, and loading. Modeling suggests that uranyl forms bidentate inner sphere

Electrochemical behavior of uranyl in anhydrous polar organic media

Energy Technology Data Exchange (ETDEWEB)

Burn, Adam G.; Nash, Kenneth L. [Washington State Univ., Pullmann, WA (United States). Dept. of Chemistry

2017-09-01

Weak complexes between pentavalent and hexavalent actinyl cations have been reported to exist in acidic, non-complexing high ionic strength aqueous media. Such ''cation-cation complexes'' were first identified in the context of actinide-actinide redox reactions in acidic aqueous media relevant to solvent extraction-based separation systems, hence their characterization is of potential interest for advanced nuclear fuel reprocessing. This chemistry could be relevant to efforts to develop advanced actinide separations based on the upper oxidation states of americium, which are of current interest. In the present study, the chemical behavior of pentavalent uranyl was examined in non-aqueous, aprotic polar organic solvents (propylene carbonate and acetonitrile) to determine whether UO{sub 2}{sup +} cations generated at the reducing working electrode surface would interact with the UO{sub 2}{sup 2+} cations in the bulk phase to form cation-cation complexes in such media. In magnesium perchlorate media, the electrolyte adsorbed onto the working electrode surface and interfered with the uranyl reduction/diffusion process through an ECE (electron transfer/chemical reaction/electron transfer) mechanism. In parallel studies of uranyl redox behavior in tetrabutylammonium hexafluorophosphate solutions, an EC (electron transfer/chemical reaction) mechanism was observed in the cyclic voltammograms. Ultimately, no conclusive electrochemical evidence demonstrated uranyl cation-cation interactions in the non-aqueous, aprotic polar organic solvent solutions, though the results reported do not completely rule out the presence of UO{sub 2}{sup +}.UO{sub 2}{sup 2+} complexes.

Barium uranyl diphosphonates

Energy Technology Data Exchange (ETDEWEB)

Nelson, Anna-Gay D., E-mail: nelsoa@umich.edu [Department of Civil Engineering and Geological Sciences and Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556 (United States); Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109-1005 (United States); Alekseev, Evgeny V. [Institute of Energy and Climate Research (IEK-6), Forschungszentrum Juelich Wilhelm-Johnen-Strasse, Juelich 52428 (Germany); Ewing, Rodney C. [Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109-1005 (United States); Albrecht-Schmitt, Thomas E. [Department of Civil Engineering and Geological Sciences and Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556 (United States)

2012-08-15

Three Ba{sup 2+}/UO{sub 2}{sup 2+} methylenediphosphonates have been prepared from mild hydrothermal treatment of uranium trioxide, methylendiphosphonic acid (C1P2) with barium hydroxide octahydrate, barium iodate monohydrate, and small aliquots of HF at 200 Degree-Sign C. These compounds, Ba[UO{sub 2}[CH{sub 2}(PO{sub 3}){sub 2}]{center_dot}1.4H{sub 2}O (Ba-1), Ba{sub 3}[(UO{sub 2}){sub 4}(CH{sub 2}(PO{sub 3}){sub 2}){sub 2}F{sub 6}]{center_dot}6H{sub 2}O (Ba-2), and Ba{sub 2}[(UO{sub 2}){sub 2}(CH{sub 2}(PO{sub 3}){sub 2})F{sub 4}]{center_dot}5.75H{sub 2}O (Ba-3) all adopt layered structures based upon linear uranyl groups and disphosphonate molecules. Ba-2 and Ba-3 are similar in that they both have UO{sub 5}F{sub 2} pentagonal bipyramids that are bridged and chelated by the diphosphonate moiety into a two-dimensional zigzag anionic sheet (Ba-2) and a one-dimensional ribbon anionic chain (Ba-3). Ba-1, has a single crystallographically unique uranium metal center where the C1P2 ligand solely bridges to form [UO{sub 2}[CH{sub 2}(PO{sub 3}){sub 2}]{sup 2-} sheets. The interlayer space of the structures is occupied by Ba{sup 2+}, which, along with the fluoride ion, mediates the structure formed and maintains overall charge balance. - Graphical abstract: Illustration of the stacking of the layers in Ba{sub 3}[(UO{sub 2}){sub 4}(CH{sub 2}(PO{sub 3}){sub 2}){sub 2})F{sub 6}]{center_dot}6H{sub 2}O viewed along the c-axis. The structure is constructed from UO{sub 7} pentagonal bipyramidal units, U(1)O{sub 7}=gray, U(2)O{sub 7}=yellow, barium=blue, phosphorus=magenta, fluorine=green, oxygen=red, carbon=black, and hydrogen=light peach. Highlights: Black-Right-Pointing-Pointer The polymerization of the UO{sub 2}{sup 2+} sites to form uranyl dimers leads to structural variations in compounds. Black-Right-Pointing-Pointer Barium cations stitch uranyl diphosphonate anionic layers together, and help mediate structure formation. Black-Right-Pointing-Pointer HF acts as both a

Production and Characterization of Desmalonichrome Relative Binding Affinity for Uranyl Ions in Relation to Other Siderophores

Energy Technology Data Exchange (ETDEWEB)

Mo, Kai-For; Dai, Ziyu; Wunschel, David S.

2016-06-24

Siderophores are Fe binding secondary metabolites that have been investigated for their uranium binding properties. Much of the previous work has focused on characterizing hydroxamate types of siderophores, such as desferrioxamine B, for their uranyl binding affinity. Carboxylate forms of these metabolites hold potential to be more efficient chelators of uranyl, yet they have not been widely studied and are more difficult to obtain. Desmalonichrome is a carboxylate siderophore which is not commercially available and so was obtained from the ascomycete fungus Fusarium oxysporum cultivated under Fe depleted conditions. The relative affinity for uranyl binding of desmalonichrome was investigated using a competitive analysis of binding affinities between uranyl acetate and different concentrations of iron(III) chloride using electrospray ionization mass spectrometry (ESI-MS). In addition to desmalonichrome, three other siderophores, including two hydroxamates (desferrioxamine B and desferrichrome) and one carboxylate (desferrichrome A) were studied to understand their relative affinities for the uranyl ion at two pH values. The binding affinities of hydroxymate siderophores to uranyl ion were found to decrease to a greater degree at lower pH as the concentration of Fe (III) ion increases. On the other hand, lowering pH has little impact on the binding affinities between carboxylate siderophores and uranyl ion. Desmalonichrome was shown to have the greatest relative affinity for uranyl at any pH and Fe(III) concentration. These results suggest that acidic functional groups in the ligands are critical for strong chelation with uranium at lower pH.

Critical experiment study on uranyl nitrate solution experiment facility

International Nuclear Information System (INIS)

Zhu Qingfu; Shi Yongqian; Wang Jinrong

2005-01-01

The Uranyl Nitrate Solution Experiment Facility was constructed for the research on nuclear criticality safety. In this paper, the configuration of the facility is introduced; a series of critical experiments on uranyl nitrate solution is described later, which were performed for various uranium concentrations under different conditions, i.e. with or without neutron absorbers in the core and with or without water-reflector outside the core. Critical volume and the minimum 235U critical mass for different uranium concentrations are presented. Finally, theoretical analysis is made on the experimental results. (authors)

79Se: geochemical and crystallo-chemical retardation mechanisms

International Nuclear Information System (INIS)

Chen, F.; Ewing, R.C.

1999-01-01

79 Se is a long-lived (1.1 x 10 6 yrs) fission product which is chemically and radiologically toxic. Under Eh-pH conditions typical of oxidative alteration of spent nuclear fuel, selenite, SeO 3 2- or HSeO 3 - or selenate, SeO 4 2- , are the dominant aqueous species of selenium. Because of the high solubility of metal-selenites and metal-selenates and the low adsorption of selenite and selenate aqueous species by geological materials under alkaline conditions, selenium may be highly mobile. However, 79 Se released from altered fuel may become immobilized by incorporation into secondary uranyl phases as low concentration impurities, and this may significantly reduce the mobility of selenium. Analysis and comparison of the known structures of uranyl phases indicate that (SeO 3 ) may substitute for (SiO 3 OH) in structures of α-uranophane and boltwoodite that are expected to be the dominant alteration products of UO 2 in Si-rich groundwater. The substitutions (SeO 3 ) (SiO 3 OH) in sklodowskite, Mg[(UO 2 )(SiO 3 OH)] 2 (H 2 O) 6 and (SeO 3 ) (PO 4 ) in phurcalite, Ca 2 [(UO 2 ) 3 (PO 4 ) 2 O 2 ](H 2 O) 7 , may occur with the eliminated apical anion being substituted for by an H 2 O group, but experimental investigation is required. The close similarity between the sheets in the structures of rutherfordine, [(UO 2 )(CO 3 )] and [(UO 2 )(SeO 3 )] implies that the substitution (SeO 3 ) (CO 3 ) can occur in rutherfordine, and possibly other uranyl carbonates. However, the substitutions: (SeO 3 ) (SiO 4 ) in soddyite and (SeO 3 ) (PO 4 ) in phosphuranylite may disrupt their structural connectivity and are, therefore, unlikely. (orig.)

Np Incorporation into Uranyl Alteration Phases: A Quantum Mechanical Approach

International Nuclear Information System (INIS)

L.C. Huller; R.C. Win; U.Ecker

2006-01-01

Neptunium is a major contributor to the long-term radioactivity in a geologic repository for spent nuclear fuel (SNF) due to its long half-life (2.1 million years). The mobility of Np may be decreased by incorporation into the U 6+ phases that form during the corrosion of SNF. The ionic radii of Np (0.089nm) and U (0.087nm) are similar, as is their chemistry. Experimental studies have shown Np can be incorporated into uranyl phases at concentrations of ∼ 100 ppm. The low concentration of Np in the uranyl phases complicates experimental detection and presents a significant challenge for determining the incorporation mechanism. Therefore, we have used quantum mechanical calculations to investigate incorporation mechanisms and evaluate the energetics of Np substituting for U. CASTEP, a density functional theory based code that uses plane waves and pseudo-potentials, was used to calculate optimal H positions, relaxed geometry, and energy of different uranyl phases. The incorporation energy for Np in uranyl alteration phases was calculated for studtite, [(UO 2 )O 2 (H 2 O) 2 ](H 2 ) 2 , and boltwoodite, HK(UO 2 )(SiO 4 )* 1.5(H 2 O). Studtite is the rare case of a stable uranyl hydroxyl-peroxide mineral that forms in the presence of H 2 O 2 from the radiolysis of H 2 O. For studtite, two incorporation mechanisms were evaluated: (1) charge-balanced substitution of Np 5+ and H + for one U 6+ , and (2) direct substitution of Np 6+ for U 6+ . For boltwoodite, the H atomic positions prior to Np incorporation were determined, as well as the Np incorporation mechanisms and the corresponding substitution energies. The preferential incorporation of Np into different structure types of U 6+ minerals was also investigated. Quantum mechanical substitution energies have to be derived at Np concentrations higher than the ones found in experiments or expected in a repository. However, the quantum mechanical results are crucial for subsequent empirical force-field and Monte

Detection of over 100 selenium metabolites in selenized yeast by liquid chromatography electrospray time-of-flight mass spectrometry.

Science.gov (United States)

Gilbert-López, Bienvenida; Dernovics, Mihaly; Moreno-González, David; Molina-Díaz, Antonio; García-Reyes, Juan F

2017-08-15

The characterization of the selenometabolome of Selenized(Se)-yeast, that is the fraction of water soluble low-molecular weight Se-metabolites produced in Se-yeast is of paramount interest to expand the knowledge on the composition of this food supplement. In this work, we have applied liquid chromatography electrospray time-of-flight mass spectrometry (LC-TOFMS) to search for Se-species from the low molecular weight range fraction of the selenized yeast used for food supplements. Prior to LC-TOFMS, sample treatment consisted of ultrasound assisted water extraction followed by size exclusion fractionation assisted with off-line inductively coupled plasma mass spectrometry detection of isotope 82 Se. The fraction corresponding to low-molecular weight species was subjected to LC-TOFMS using electrospray ionization in the positive ion mode. The detection of the suspected selenized species has been based on the information obtained from accurate mass measurements of both the protonated molecules and fragments from in-source CID fragmentation; along with the characteristic isotope pattern exhibited by the presence of Se. The approach enables the detection of 103 selenized species, most of them not previously reported, in the range from ca. 300-650Da. Besides the detection of selenium species, related sulphur derivate metabolites were detected based on the accurate mass shift due to the substitution of sulphur and selenium. Copyright © 2017. Published by Elsevier B.V.

Influence of Se concentrations and species in hydroponic cultures on Se uptake, translocation and assimilation in non-accumulator ryegrass.

Science.gov (United States)

Versini, Antoine; Di Tullo, Pamela; Aubry, Emmanuel; Bueno, Maïté; Thiry, Yves; Pannier, Florence; Castrec-Rouelle, Maryse

2016-11-01

The success of biofortification and phytoremediation practices, addressing Se deficiency and Se pollution issues, hinges crucially on the fate of selenium in the plant media in response to uptake, translocation and assimilation processes. We investigate the fate of selenium in root and shoot compartments after 3 and 6 weeks of experiment using a total of 128 plants grown in hydroponic solution supplied with 0.2, 2, 5, 20 and 100 mg L -1 of selenium in the form of selenite, selenate and a mixture of both species. Selenate-treated plants exhibited higher root-to-shoot Se translocation and total Se uptake than selenite-treated plants. Plants took advantage of the selenate mobility and presumably of the storage capacity of leaf vacuoles to circumvent selenium toxicity within the plant. Surprisingly, 28% of selenate was found in shoots of selenite-treated plants, questioning the ability of plants to oxidize selenite into selenate. Selenomethionine and methylated organo-selenium amounted to 30% and 8% respectively in shoots and 35% and 9% in roots of the identified Se, suggesting that selenium metabolization occurred concomitantly in root and shoot plant compartments and demonstrating that non-accumulator plants can synthesize notable quantities of precursor compound for volatilization. The present study demonstrated that non-accumulator plants can develop the same strategies as hyper-accumulator plants to limit selenium toxicity. When both selenate and selenite were supplied together, plants used selenate in a storage pathway and selenite in an assimilation pathway. Plants might thereby benefit from mixed supplies of selenite and selenate by saving enzymes and energy required for selenate reduction. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Uranyl oxalate hydrates: structures and IR spectra

International Nuclear Information System (INIS)

Giesting, P.A.; Porter, N.J.; Burns, P.C.

2006-01-01

The novel compound (UO 2 ) 2 C 2 O 4 (OH) 2 (H 2 O) 2 (UrOx2A) and the previously studied compound UO 2 C 2 O 4 (H 2 O) 3 (UrOx3) have been synthesized by mild hydrothermal methods. Single crystal diffraction data collected at 125 K using MoK α radiation and a CCD-based area detector were used to solve and refine the crystal structures by full-matrix least-squares techniques to agreement indices (UrOx2A, UrOx3) wR 2 = 0.037, 0.049 for all data, and R1 0.015, 0.024 calculated for 1285, 2194 unique reflections respectively. The compound UrOx2A is triclinic, space group P1, Z = 1, a = 5.5353(4), b 6.0866(4), c = 7.7686(6) Aa, α = 85.6410(10) , β = 89.7740(10) , γ = 82.5090(10) , V = 258.74(3) Aa 3 . The compound UrOx3 is monoclinic, space group P2 1 /c, Z = 4, a = 5.5921(4), b = 16.9931(13), c = 9.3594(7) Aa, β = 99.5330(10) , V = 877.11(11) Aa 3 . The structures consist of chains of uranyl pentagonal bipyramids connected by oxalate groups and, in UrOx2A, hydroxyl groups; UrOx2A is also notable for its high (2:1) ratio of uranyl to oxalate groups, higher than any observed in other published structures of uranyl oxalates. The structure determined for UrOx3, previously studied by Jayadevan and Chackraburtty (1972); Mikhailov et al. (1999) is in agreement with the previous results; however, the increased precision of the present low-temperature structure refinement allows for the assignment of H atom positions based on the difference Fourier map of electron density. The infrared spectra of these two materials collected at room temperature are also presented and compared with previous work on uranyl oxalate systems. (orig.)

In situ characterization of organo-modified and unmodified montmorillonite aqueous suspensions by UV-visible spectroscopy.

Science.gov (United States)

Alin, Jonas; Rubino, Maria; Auras, Rafael

2015-10-15

UV-visible (UV-Vis) spectroscopy (Tyndall spectra) was applied and tested for its ability to measure organo-modified and unmodified montmorillonite (MMT) clays in aqueous suspensions. A full factorial design of experiments was used to study the influence of pH, NaCl and clay concentrations on the average particle size of the clay agglomerates. The methodology was evaluated by observing results that were consistent with previous research about the unmodified clay's behavior in aqueous suspensions. The results from this evaluation corresponded to accepted theories about the unmodified clay's behavior, indicating that the methodology is precise enough to distinguish the effects of the studied factors on these clay suspensions. The effect of clay concentration was related to the amount of ions per clay particle for the unmodified clay, but was not significant for the organo-modified MMT. The average particle size of the organo-modified MMT in suspension was significantly larger than that of the unmodified clay. Size of the organo-modified MMT agglomerates in suspension decreased in the presence of NaCl and at both high and low pH; this behavior was opposite to that of the unmodified clay. These results demonstrate that the UV-Vis methodology is well-suited for characterizing clay particle size in aqueous suspensions. The technique also is simple, rapid, and low-cost. Copyright © 2015 Elsevier Inc. All rights reserved.

Innovative Uses of Organo-philic Clays for Remediation of Soils, Sediments and Groundwater

International Nuclear Information System (INIS)

Bullock, A.M.

2009-01-01

PCBs and similar low-solubility organic compounds continue to offer significant challenges in terrestrial and sediment remediation applications. While selective media such as granular activated carbon (GAC) have proven to be successful at absorbing soluble organics, these media may have reduced performance due to blinding in the presence of high molecular weight organic matter. An alternative technology addresses this problem with a clay-based adsorption media, which effectively and efficiently stabilizes low-solubility organic matter. Organoclay TM reactive media utilizes granular sodium bentonite, which has been chemically modified to attract organic matter without absorbing water. The unique platelet structure of bentonite clays provides tremendous surface area and the capacity of the media to absorb over 60 percent of its own weight in organic matter. Because of these properties, organo-clays allow for several cost-effective in-situ remediation techniques, such as: - Flow-through filtration for removal of organic matter from aqueous solutions. Organo-clay can be utilized as a fixed-bed media in a column operation. This specialty media offers a high efficient alternative to Granular Activated Carbon (GAC) when applied as a flow through media to remove oil, PCB and other low soluble organic contaminates from water. - Placement in a Reactive Core Mat TM . Organo-clay may be encapsulated into carrier textiles which are adhered together to create a thin reactive layer with high strength and even distribution of the reactive media. This type of delivery mechanism can be successfully applied in a sub aqueous or terrestrial environment for sediment capping applications - Permeable reactive barriers. Organo-clay can deliver high sorption capacity, high efficiency, and excellent hydraulic conductivity as a passive reactive media in these applications. (authors)

Effect of Sodium Selenate on Hippocampal Proteome of 3×Tg-AD Mice-Exploring the Antioxidant Dogma of Selenium against Alzheimer's Disease.

Science.gov (United States)

Iqbal, Javed; Zhang, Kaoyuan; Jin, Na; Zhao, Yuxi; Liu, Qiong; Ni, Jiazuan; Shen, Liming

2018-04-19

Selenium (Se), an antioxidant trace element, is an important nutrient for maintaining brain functions and is reported to be involved in Alzheimer's disease (AD) pathologies. The present study has been designed to elucidate the protein changes in hippocampus of 3×Tg-AD mice after supplementing sodium selenate as an inorganic source of selenium. By using iTRAQ proteomics technology, 113 differentially expressed proteins (DEPs) are found in AD/WT mice with 37 upregulated and 76 downregulated proteins. Similarly, in selenate-treated 3×Tg-AD (ADSe/AD) mice, 115 DEPs are found with 98 upregulated and 17 downregulated proteins. The third group of mice (ADSe/WT) showed 75 DEPs with 46 upregulated and 29 downregulated proteins. Among these results, 42 proteins (40 downregulated and 2 upregulated) in the diseased group showed reverse expression when treated with selenate. These DEPs are analyzed with different bioinformatics tools and are found associated with various AD pathologies and pathways. Based on their functions, selenate-reversed proteins are classified as structural proteins, metabolic proteins, calcium regulating proteins, synaptic proteins, signaling proteins, stress related proteins, and transport proteins. Six altered AD associated proteins are successfully validated by Western blot analysis. This study shows that sodium selenate has a profound effect on the hippocampus of the triple transgenic AD mice. This might be established as an effective therapeutic agent after further investigation.

Rapid fabrication of self-ordered porous alumina with 10-/sub-10-nm-scale nanostructures by selenic acid anodizing

Science.gov (United States)

Nishinaga, Osamu; Kikuchi, Tatsuya; Natsui, Shungo; Suzuki, Ryosuke O.

2013-01-01

Anodic porous alumina has been widely investigated and used as a nanostructure template in various nanoapplications. The porous structure consists of numerous hexagonal cells perpendicular to the aluminum substrate and each cell has several tens or hundreds of nanoscale pores at its center. Because the nanomorphology of anodic porous alumina is limited by the electrolyte during anodizing, the discovery of additional electrolytes would expand the applicability of porous alumina. In this study, we report a new self-ordered nanoporous alumina formed by selenic acid (H2SeO4) anodizing. By optimizing the anodizing conditions, anodic alumina possessing 10-nm-scale pores was rapidly assembled (within 1 h) during selenic acid anodizing without any special electrochemical equipment. Novel sub-10-nm-scale spacing can also be achieved by selenic acid anodizing and metal sputter deposition. Our new nanoporous alumina can be used as a nanotemplate for various nanostructures in 10-/sub-10-nm-scale manufacturing. PMID:24067318

Investigation of uranyl sorbed to Wyoming montmorillonite at amphoteric and exchange sites by optical spectroscopy

International Nuclear Information System (INIS)

Morris, D.E.; Chisholm-Brause, C.J.; Berg, J.M.; McKinley, J.P.; Zachara, J.M.; Smith, S.C.

1993-01-01

Using optical spectroscopy, the authors have characterized aqueous uranyl (UO 2 2+ ) sorption complexes on a sodium-saturated Wyoming montmorillonite (SWy-1) at low and high ionic strength (IS, as NaClO 4 . McKinley et al. (1193), ACS Spring Meeting) have shown that uranyl uptake is suppressed at high IS at these pH values, reflecting increased cation competition for exchange sites, and an increase in the ratio of uranyl species sorbed on amphoteric edge sites to those in exchange sites. At higher pH, sorption is less dependent on IS, with complexation by amphoteric edge sites becoming dominant as pH increases. At low pH, emission spectra for uranyl sorbed to SWy-1 from solutions with high IS ([Na]/[U] > 1000) are distinct from those at low IS ([Na]/[U] < 10). The low IS spectra are dominanted by a short lifetime component (τ∼0.5μs), and have low integrated intensities (normalized for uranium concentration). However, gated detection clearly resolves an additional, longer-loved component. The high IS spectra have significant contributions form 2-3 longer-lived components (5<τ120μs), and have much stronger intensities. Based on comparison to solution data, these results suggest that the uranyl moiety in the exchange sites is strikingly similar to the fully aquated uranyl monomer in solution, whereas the uranyl species occupying the edge sites are structurally more similar to hydrolyzed uranyl species in solution. At higher pH values, the emission spectra represent composites of at least the two distinct spectra identified at lower pH. However, the ratios of the different components and thus the overall emission spectra vary as a function of ionic strength. These results demonstrate that several spectroscopically (and therefore structurally) distinct sorption complexes exist in exchange and edges of SWy-1

Contribution to the study of uranyl salts in butyl phosphate solutions; Contribution a l'etude des solutions de sels d'uranyle dans les phosphates butyliques

Energy Technology Data Exchange (ETDEWEB)

Coulon, A. [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

1965-06-01

A spectroscopic study in the normal infrared region and involving the following associations: tri-alkyl phosphates (tri-butyl, tri-ethyl, tri-methyl), uranyl salts (nitrate, chloride, acetate) has confirmed the existence of an interaction between the phosphoryl group and the uranium atom, as shown by a movement of absorption band for the valency P = 0 from {approx} 1270 cm{sup -1} to {approx} 1180 cm{sup -1}. A study of the preparation, analysis and spectroscopy of the solids obtained by the precipitation of uranyl salts by acid butyl phosphates has been carried out. By infrared spectrophotometry it has been shown that the tri-butyl and di-butyl phosphates are associated in non-polar diluents even before the uranium is introduced. The extraction of uranyl salts from acid aqueous solutions by a diluted mixture of tri-butyl and di-butyl phosphates proceeds by different mechanisms according to the nature of the ion (nitrate or chloride). (author) [French] Une etude spectroscopique dans l'infrarouge moyen portant sur les associations: - phosphates trialcoyliques (tributylique - triethylique - trimethylique) - sels d'uranyle (nitrate, chlorure, acetate) a confirme l'existence d'une interaction entre le groupement phosphoryle et l'atome d'uranium, se manifestant par un deplacement de la bande d'absorption de la vibration de valence P = 0 de {approx} 1270 cm{sup -1} a {approx} 1180 cm{sup -1}. Une etude preparative, analytique et spectroscopique des solides obtenus par precipitation de sels d'uranyle par les phosphates butyliques acides a ete effectuee. La spectrophotomerie infrarouge met en evidence l'association, anterieure a toute introduction d'uranium, des phosphates tributylique et dibutylique dans des diluants non polaires. L'extraction de sels d'uranyle, d'une solution aqueuse acide par un melange dilue de phosphates tributylique et dibutylique, s'effectue suivant des processus differents a la

Miscellaneous Lasing Actions in Organo-Lead Halide Perovskite Films.

Science.gov (United States)

Duan, Zonghui; Wang, Shuai; Yi, Ningbo; Gu, Zhiyuan; Gao, Yisheng; Song, Qinghai; Xiao, Shumin

2017-06-21

Lasing actions in organo-lead halide perovskite films have been heavily studied in the past few years. However, due to the disordered nature of synthesized perovskite films, the lasing actions are usually understood as random lasers that are formed by multiple scattering. Herein, we demonstrate the miscellaneous lasing actions in organo-lead halide perovskite films. In addition to the random lasers, we show that a single or a few perovskite microparticles can generate laser emissions with their internal resonances instead of multiple scattering among them. We experimentally observed and numerically confirmed whispering gallery (WG)-like microlasers in polygon shaped and other deformed microparticles. Meanwhile, owing to the nature of total internal reflection and the novel shape of the nanoparticle, the size of the perovskite WG laser can be significantly decreased to a few hundred nanometers. Thus, wavelength-scale lead halide perovskite lasers were realized for the first time. All of these laser behaviors are complementary to typical random lasers in perovskite film and will help the understanding of lasing actions in complex lead halide perovskite systems.

Cs2SeO4-UO2SeO4-H2O system at 25 deg C

International Nuclear Information System (INIS)

Serezhkina, L.B.; Serezhkin, V.N.

1987-01-01

Using the method of isothermal solubility at 25 deg C the interaction of cesium and uranyl selenates in aqueous solution is studied. Formation of congruently soluble Cs 2 UO 2 (SeO 4 ) 2 x2H 2 O and Cs 2 (UO 2 ) 2 x(SeO 4 ) 3 is ascertained, their crystallographic characteristics being determined

Preparation and thermogravimetric study of some uranyl phosphates

International Nuclear Information System (INIS)

Schaekers, J.M.

1970-10-01

The preparation of uranyl ammonium phosphate trihydrate (UAP = UO 2 NH 4 PO 4 .3H 2 O), acid uranyl phosphate tetrahydrate(AUP = UO 2 HPO 4 .4H 2 O) and neutral uranyl phosphate tetrahydrate (NUPT = (UO 2 ) 3 (PO 4 ) 2 .4H 2 O) was investigated during the data from the literature. The thermal decomposition in different atmospheres, such as air, oxygen, nitrogen and argon, was studied in the temperature range 25-1000 0 C. It was found that the pyrophosphate U 2 O 3 P 2 O 7 is a stable decomposition product of UAP as well as of AUP. A mixture of U 3 O 8 and U 2 O 3 P 2 O 7 is obtained when the NUPT is decomposed in an oxygen-free atmosphere. NUPT however is stable in an oxidising atmosphere. Hydrogen and carbon reductions were also carried out, and UO 2 or (UO) 2 P 2 O 7 as well as mixtures of these two products can be obtained, depending on the starting material and the reduction temperature. The different reduction and decomposition reactions were studied by means of thermogravimetric analysis, and activation energies were calculated where possible. I.R. spectral analysis was also used to identify various products with the same composition [af

Corrosion resistance of cement brick on an organo-mineral base in a hydrogen sulfide medium

Energy Technology Data Exchange (ETDEWEB)

Potapov, A G; Belousov, G A; Pustovalov, V I; Skorikov, B M

1981-01-01

Results are presented of strength tests of cement brick made of different types of cement as a function of the composition of the mixing liquid and storage conditions. It is established that cement brick made of cement on a cinder base mixed in hydrogen sulfide water possesses the highest corrosive resistance to hydrogen sulfide attack. A marked increase in corrosion resistance is observed in cement brick on an organo-mineral base. Results of industrial tests of organo-mineral grouting mortar in a hydrogen sulfide medium are demonstrated.

Engineering of specific uranyl-coordination sites in the calcium-binding motif of Calmodulin

International Nuclear Information System (INIS)

Beccia, M.; Pardoux, R.; Sauge-Merle, S.; Bremond, N.; Lemaire, D.; Berthomieu, C.; Delangle, P.; Guilbaud, P.

2014-01-01

Complete text of publication follows: Characterization of heavy metals interactions with proteins is fundamental for understanding the molecular factors and mechanisms governing ions toxicity and speciation in cells. This line of research will also help in developing new molecules able to selectively and efficiently bind toxic metal ions, which could find application for bio-detection or bioremediation purposes. We have used the regulatory calcium-binding protein Calmodulin (CaM) from A. thaliana as a structural model and, starting from it, we have designed various mutants by site-directed mutagenesis. We have analysed thermodynamics of uranyl ion binding to both sites I and II of CaM N-terminal domain and we have identified structural factors governing this interaction. Selectivity for uranyl ion has been tested by studying reactions of the investigated peptides with Ca 2+ , in the same conditions used for UO 2 2+ . Spectro-fluorimetric titrations and FTIR analysis have shown that the affinity for uranyl increases by phosphorylation of a threonine in site I, especially approaching the physiological pH, where the phospho-threonine side chain is deprotonated. Based on structural models obtained by Molecular Dynamics, we tested the effect of a two residues deletion on site I properties. We obtained an almost two orders of magnitude increase in affinity for uranyl, with a sub-nanomolar dissociation constant for the uranyl complex with the non phosphorylated peptide, and an improved uranyl/calcium selectivity. Allosteric effects depending on Ca 2+ and UO 2 2+ binding have been investigated by comparing thermodynamic parameters obtained for mutants having both sites I and II able to chelate metal ions with those of mutants consisting of just one active site

Silver-organo-complex ink with high conductivity and inkjet stability

KAUST Repository

Vaseem, Mohammad

2017-06-22

A robust formulation of silver-organo-complex (SOC) ink and method of making same are provided. In an aspect, the complexing molecules act as reducing agents. The silver loaded ink can be printed and sintered on a wide range of substrates with uniform surface morphology and excellent adhesion.

Silver-organo-complex ink with high conductivity and inkjet stability

KAUST Repository

Vaseem, Mohammad; McKerricher, Garret; Shamim, Atif

2017-01-01

A robust formulation of silver-organo-complex (SOC) ink and method of making same are provided. In an aspect, the complexing molecules act as reducing agents. The silver loaded ink can be printed and sintered on a wide range of substrates with uniform surface morphology and excellent adhesion.

Thermodynamics of Uranyl Minerals: Enthalpies of Formation of Uranyl Oxide Hydrates

Energy Technology Data Exchange (ETDEWEB)

K. Kubatko; K. Helean; A. Navrotsky; P.C. Burns

2005-05-11

The enthalpies of formation of seven uranyl oxide hydrate phases and one uranate have been determined using high-temperature oxide melt solution calorimetry: [(UO{sub 2}){sub 4}O(OH){sub 6}](H{sub 2}O){sub 5}, metaschoepite; {beta}-UO{sub 2}(OH){sub 2}; CaUO{sub 4}; Ca(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 8}, becquerelite; Ca(UO{sub 2}){sub 4}O{sub 3}(OH){sub 4}(H{sub 2}O){sub 2}; Na(UO{sub 2})O(OH), clarkeite; Na{sub 2}(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 7}, the sodium analogue of compreignacite and Pb{sub 3}(UO{sub 2}){sub 8}O{sub 8}(OH){sub 6}(H{sub 2}O){sub 2}, curite. The enthalpy of formation from the binary oxides, {Delta}H{sub f-ox}, at 298 K was calculated for each compound from the respective drop solution enthalpy, {Delta}H{sub ds}. The standard enthalpies of formation from the elements, {Delta}H{sub f}{sup o}, at 298 K are -1791.0 {+-} 3.2, -1536.2 {+-} 2.8, -2002.0 {+-} 3.2, -11389.2 {+-} 13.5, -6653.1 {+-} 13.8, -1724.7 {+-} 5.1, -10936.4 {+-} 14.5 and -13163.2 {+-} 34.4 kJ mol{sup -1}, respectively. These values are useful in exploring the stability of uranyl oxide hydrates in auxiliary chemical systems, such as those expected in U-contaminated environments.

Ligand exchange in uranyl complexes in non-aqueous solutions: equilibrium properties

International Nuclear Information System (INIS)

Egozy, Y.; Weiss, S.

1976-01-01

The systems uranyl nitrate, tributylphosphate and 8-hydroxyquinoline or diphenylcarbazone were studied in chloroform, carbon tetrachloride and 1,2-dichloroethane at a number of temperatures. The nature of the complexes formed was determined and the equilibrium constants and several thermodynamic functions were measured. 8-hydroxyquinoline and diphenylcarbazone will be valuable as indicators for uranyl in kinetic studies. They are also interesting since they participate, along with tributylphosphate, in formation of synergistic complexes. (author)

Uranyl adsorption kinetics within silica gel: dependence on flow velocity and concentration

Science.gov (United States)

Dodd, Brandon M.; Tepper, Gary

2017-09-01

Trace quantities of a uranyl dissolved in water were measured using a simple optical method. A dilute solution of uranium nitrate dissolved in water was forced through nanoporous silica gel at fixed and controlled water flow rates. The uranyl ions deposited and accumulated within the silica gel and the uranyl fluorescence within the silica gel was monitored as a function of time using a light emitting diode as the excitation source and a photomultiplier tube detector. It was shown that the response time of the fluorescence output signal at a particular volumetric flow rate or average liquid velocity through the silica gel can be used to quantify the concentration of uranium in water. The response time as a function of concentration decreased with increasing flow velocity.

Selen og vitamin E til søer og pattegrise

DEFF Research Database (Denmark)

Nielsen, H. E.; Danielsen, V.; Simesen, M. G.

1977-01-01

Formålet med dette forsøg var at undersøge virkningen af foderets selen- og vitamin E indhold på søernes frugtbarhed og pattegrisenes levedygtighed og vækst. Endvidere at undersøge koncentrationen af selen (Se) og vitamin E i råmælk, somælk og blod i relation til foderet. Der forekom enkelte...... dødsfald blandt grisene, som kunne sættes i forbindelse med enten lavt Se-indhold eller lavt vitamin E indhold i foderet. Der blev desuden konstateret flere brunst- og drægtighedsproblemer hos søer, derfik foder med det lave indhold af vitamin E end hos søer i de andre grupper. En forøgelse af Se......-indholdet fra 30 til 60 µg pr. kg foder gav en fordobling af indholdet i råmælk og i somælk. En forøgelse af vitamin E indholdet i foderet fra ca. 20 mg til ca. 45 mg pr. kg foder gav 4 gange forøgelse i råmælk og somælk. Der blev konstateret tilsvarende virkninger af Se og vitamin E i foderet på indholdet i...

Inhibition Mechanism of Uranyl Reduction Induced by Calcium-Carbonato Complexes

Science.gov (United States)

Jones, M. E.; Bargar, J.; Fendorf, S. E.

2015-12-01

Uranium mobility in the subsurface is controlled by the redox state and chemical speciation, generally as minimally soluble U(IV) or soluble U(VI) species. In the presence of even low carbonate concentrations the uranyl-carbonato complex quickly becomes the dominant aqueous species; they are, in fact, the primary aqueous species in most groundwaters. Calcium in groundwater leads to ternary calcium-uranyl-carbonato complexes that limit the rate and extent of U(VI) reduction. This decrease in reduction rate has been attributed to surface processes, thermodynamic limitations, and kinetic factors. Here we present a new mechanism for the inhibition of ferrous iron reduction of uranyl-carbonato species in the presence of calcium. A series of experiments under variable Ca conditions were preformed to determine the role of Ca in the inhibition of U reduction by ferrous iron. Calcium ions in the Ca2UO2(CO3)3 complex sterically prevent the interaction of Fe(II) with U(VI), in turn preventing the Fe(II)-U(VI) distance required for electron transfer. The mechanism described here helps to predict U redox transformations in suboxic environments and clarifies the role of Ca in the fate and mobility of U. Electrochemical measurements further show the decrease of the U(VI) to U(V) redox potential of the uranyl-carbonato complex with decreasing pH suggesting the first electron transfer is critical determining the rate and extent of uranium reduction.

Isolation of a star-shaped uranium(V/VI) cluster from the anaerobic photochemical reduction of uranyl(VI)

International Nuclear Information System (INIS)

Chatelain, Lucile; White, Sarah; Scopelliti, Rosario; Mazzanti, Marinella

2016-01-01

Actinide oxo clusters are an important class of compounds due to their impact on actinide migration in the environment. The photolytic reduction of uranyl(VI) has potential application in catalysis and spent nuclear fuel reprocessing, but the intermediate species involved in this reduction have not yet been elucidated. Here we show that the photolysis of partially hydrated uranyl(VI) in anaerobic conditions leads to the reduction of uranyl(VI), and to the incorporation of the resulting U V species into the stable mixed-valent star-shaped U VI /U V oxo cluster [U(UO 2 ) 5 (μ 3 -O) 5 (PhCOO) 5 (Py) 7 ]. This cluster is only the second example of a U VI /U V cluster and the first one associating uranyl groups to a non-uranyl(V) center. The U V center in 1 is stable, while the reaction of uranyl(V) iodide with potassium benzoate leads to immediate disproportionation and formation of the U 12 IV U 4 V O 24 cluster {[K(Py) 2 ] 2 [K(Py)] 2 [U 16 O 24 (PhCOO) 24 (Py) 2 ]}.

Contribution to the study of the evaporation of aqueous uranyl nitrate solutions; Contribution a l'etude de l'evaporation des solutions aqueuses de nitrate d'uranyle

Energy Technology Data Exchange (ETDEWEB)

Billy, J [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

1967-05-15

This work was carried out with a view to define the conditions under which is affected the concentration of aqueous uranyl nitrate solutions one of the steps in uranium extraction metallurgy. The first port is devoted to the experimental determination of the physical characteristics of aqueous uranyl nitrate solutions, from dilute to concentrated solutions. The second part of this work is devoted to the isothermal evaporation of solution a west ted-wall column; this chemical engineering study has been more particularly devoted to the definition of the influence of the dynamics of the liquid phase on the exchange of matter between the two phases in contact. (author) [French] La concentration par evaporation des solutions aqueuses de nitrate d'uranyle constitue une etape de la metallurgie de l'uranium dont ce travail a voulu preciser la connaissance. Dans ce but, une premiere partie a ete consacree a la determination experimentale de caracteristiques physiques des solutions aqueuses de nitrate d'uranyle, des solutions diluees aux solutions saturees. Dans une deuxieme partie, ce travail a porte sur l'evaporation isotherme des solutions dans une colonne a paroi mouillee; cette etude de genie chimique a ete plus particulierement orientee de facon a preciser l'influence de la dynamique de la phase liquide sur l'echange de matiere entre les deux phases en contact. (auteur)

Preparation and properties of organo(acetylacetonato)antimony(V) compounds

NARCIS (Netherlands)

Meinema, H.A.; Noltes, J.G.

Organo(acetylacetonato)antimony(V) compounds of the types R2SbCl2Acac, R4SbAcac, PhSbCl3Acac and Cl4SbAcac have been synthesized. The compounds are monomeric in solution. IR and PMR data of these compounds, which contain a chelated Acac ligand have been discussed. Ph2SbCl2Acac shows abnormal

Observation of Radiolytic Field Alteration of the Uranyl Cation in Bicarbonate Solution

Energy Technology Data Exchange (ETDEWEB)

Snow, Lanee A.; McNamara, Bruce K.; Sinkov, Sergey I.; Cho, Herman M.; Friese, Judah I.

2006-12-01

In previous work we demonstrated that radiolysis of uranyl tris carbonate in near neutral pH to alkaline carbonate solutions, could be followed by 13C NMR. Radiolysis of the complex produced novel uranyl peroxo carbonate solution state species, whose structures depended on the pH and radiolytic dose rate. In this work, we investigate speciation of the uranyl carbonate trimer which is predominant in bicarbonate solution near pH 5.9. We observe radiolytically derived speciation to different mixed peroxy carbonate species than seen in the higher pH solutions. Auto radiolysis of uranium (VI) carbonate solutions between pH 5.9 and 7.2 is shown to alter the uranium speciation over relatively short periods of time and was followed by 13C NMR and visible spectrophotometry, using dissolved 233(UO2)3(CO3)6 6- both as the radiolysis source (D= 14.9 Gy/hr) and as a trap for the newly formed hydrogen peroxide. Direct addition of hydrogen peroxide to solutions of the uranyl-carbonate trimer is shown to reproduce the 13 C NMR signatures of the complexe(s) formed by radiolysis, but additionally a variety of new complexes are revealed. Ratios of H2O2/trimer < 1.5 produced a uranyl peroxo carbonate adduct, that is shown to be common to the radiolytically produced species. Ratios of H2O2/ trimer >1 resulted in formation of stable higher order peroxo carbonate complexes. The 13C NMR signatures and visible spectra of these complexes are described here. Rigorous characterization of the species is an ongoing effort.

Growth of uranyl hydroxide nanowires and nanotubes with electrodeposition method

International Nuclear Information System (INIS)

Wang Lin; Yuan Liyong; Chai Zhifang; Shi Weiqun

2013-01-01

Actinides nanomaterials have great potential applications in fabrication of novel nuclear fuel and spent fuel reprocessing in advanced nuclear energy system. However, the relative research so far still lacks systematic investigation on the synthetic methods for actinides nanomaterials. In this work, we use track-etched membranes as hard templates to synthesize uranium based nanomaterials with novel structures by electrodeposition method. Through electrochemical behavior investigations and subsequent product characterizations such as energy dispersive spectrometer (EDS), fourier transform infrared spectroscopy (FTIR), the chemical composition of deposition products have been confirmed as the uranyl hydroxide. More importantly, accurate control of morphology and structures (nanowires and nanotubes) could be achieved by carefully adjusting the growth parameters such as deposition time and deposition current density. It was found that the preferred morphology of electrodeposition products is nanowire when a low current density was applied, whereas nanotubes could be formed only under conditions of high current density and the short deposition time. The mechanism for the formation of nanowires in track-etched membranes is based on the precipitation of uranyl hydroxide from uranyl nitrate solution, according to the previous researches about obtaining nanostructures of hydroxides from nitrate salt solutions. And we have concluded that the formation of nanotubes is attributed to the hydrogen bubbles generated by water electrolysis under the condition of over-potential electro-reduction. The conveying of hydrogen bubbles plays the role of dynamic template which can prevent the complete filling of uranyl hydroxide in the channels. Additionally, we transform the chemical composition of deposition products from uranyl hydroxide to triuranium octoxide by calcining them at 500 and 800 degree centigrade, respectively, and SEM results show the morphologies of nanowires and

Standard test method for isotopic analysis of hydrolyzed uranium hexafluoride and uranyl nitrate solutions by thermal ionization mass spectrometry

CERN Document Server

American Society for Testing and Materials. Philadelphia

2005-01-01

1.1 This method applies to the determination of isotopic composition in hydrolyzed nuclear grade uranium hexafluoride. It covers isotopic abundance of 235U between 0.1 and 5.0 % mass fraction, abundance of 234U between 0.0055 and 0.05 % mass fraction, and abundance of 236U between 0.0003 and 0.5 % mass fraction. This test method may be applicable to other isotopic abundance providing that corresponding standards are available. 1.2 This test method can apply to uranyl nitrate solutions. This can be achieved either by transforming the uranyl nitrate solution to a uranyl fluoride solution prior to the deposition on the filaments or directly by depositing the uranyl nitrate solution on the filaments. In the latter case, a calibration with uranyl nitrate standards must be performed. 1.3 This test method can also apply to other nuclear grade matrices (for example, uranium oxides) by providing a chemical transformation to uranyl fluoride or uranyl nitrate solution. 1.4 This standard does not purport to address al...

Combination cancer treatment through photothermally controlled release of selenous acid from gold nanocages.

Science.gov (United States)

Cheng, Haoyan; Huo, Da; Zhu, Chunlei; Shen, Song; Wang, Wenxia; Li, Haoxuan; Zhu, Zhihong; Xia, Younan

2018-04-03

Selenite, one of the inorganic forms of selenium, is emerging as an attractive chemotherapeutic agent owing to its selectivity in eradicating cancer cells. Here we demonstrate a new formulation of nanomedicine based on selenous acid, which is mixed with lauric acid (a phase-change material with a melting point around 43 °C) and then loaded into the cavities of Au nanocages. The Au nanocages can serve as a carrier during cell endocytosis and then as a photothermal agent to melt the lauric acid upon the irradiation with a near-infrared laser, triggering the swift release of selenous acid. The photothermal and chemo therapies can also work synergistically, leading to enhanced destruction of cancer cells relative to normal cells. Our systematic study suggests that the impaired mitochondrial function arising from the ROS generated through combination treatment is responsible for the cell death. This study offers an appealing candidate that holds great promise for synergistic cancer treatment. Published by Elsevier Ltd.

Effect of selenization conditions on the growth and properties of Cu2ZnSn(S,Se)4 thin films

OpenAIRE

Ranjbar, Samaneh; Rajesh Menon, M.R.; Fernandes, P.A.; da Cunha, A.F.

2015-01-01

The opto-electronic properties of copper zinc tin sulfide can be tuned to achieve better cell efficiencies by controlled incorporation of selenium. In this paper we report the growth of Cu2ZnSn(S,Se)4 (CZTSSe) using a hybrid process involving the sequential evaporation of Zn and sputtering of the sulfide precursors of Cu and Sn, followed by a selenization step. Two approaches for selenization were followed, one using a tubular furnace and the other using a rapid thermal processor. The effects...

The intensity of tyrosine nitration is associated with selenite and selenate toxicity in Brassica juncea L.

Science.gov (United States)

Molnár, Árpád; Feigl, Gábor; Trifán, Vanda; Ördög, Attila; Szőllősi, Réka; Erdei, László; Kolbert, Zsuzsanna

2018-01-01

Selenium phytotoxicity involves processes like reactive nitrogen species overproduction and nitrosative protein modifications. This study evaluates the toxicity of two selenium forms (selenite and selenate at 0µM, 20µM, 50µM and 100µM concentrations) and its correlation with protein tyrosine nitration in the organs of hydroponically grown Indian mustard (Brassica juncea L.). Selenate treatment resulted in large selenium accumulation in both Brassica organs, while selenite showed slight root-to-shoot translocation resulting in a much lower selenium accumulation in the shoot. Shoot and root growth inhibition and cell viability loss revealed that Brassica tolerates selenate better than selenite. Results also show that relative high amounts of selenium are able to accumulate in Brassica leaves without obvious visible symptoms such as chlorosis or necrosis. The more severe phytotoxicity of selenite was accompanied by more intense protein tyrosine nitration as well as alterations in nitration pattern suggesting a correlation between the degree of Se forms-induced toxicities and nitroproteome size, composition in Brassica organs. These results imply the possibility of considering protein tyrosine nitration as novel biomarker of selenium phytotoxicity, which could help the evaluation of asymptomatic selenium stress of plants. Copyright © 2017 Elsevier Inc. All rights reserved.

Preparation and properties of uranyl bromate monohydrate

International Nuclear Information System (INIS)

Weigel, F.

1983-01-01

Uranyl bromate monohydrate UO 2 (BrO 3 ) 2 .H 2 O was obtained as a greenish-yellow solid by the metathesis of a uranyl sulfate solution with a stoichiometric amount of barium bromate solution. On evaporation of the supernatant of the precipitated BaSO 4 a greenish-yellow syrup was obtained which, on dehydration with anhydrous carbon tetrachloride, yielded a free-flowing greenish-yellow powder with stoichiometry UO 2 (BrO 3 ) 2 .H 2 O. Powder diffraction diagrams of UO 2 (BrO 3 ) 2 .H 2 O obtained using the Guinier method yielded an orthorhombic lattice (space group, Pbcn (no. 60)) with a = 8.533 +- 0.003 A, b = 7.639 +- 0.003 A and c = 12.293 +- 0.004 A; the X-ray density was 4.507 g cm -3 . The compound was characterized by chemical analysis, IR spectroscopy and differential thermal analysis. (Auth.)

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

The thermal denigration in fluid-bed to make uranyl product

International Nuclear Information System (INIS)

Ma Zhenrong; Cui Yulin; Zhu Changbing; Fan Chuanyong; Liu Yanfeng

2010-01-01

Nuclear fuel reprocessing plant used the thermal denigration to high concentration of uranyl nitrate solution in fluid-bed to make uranyl product. First the uranyl nitrate solution were concentrated in evaporator, into 300 gU/L, 600 gU/L, 750 gU/L and 1000 gU/L.When the fluid-bed was in good fluidity state at 320 degree C, the solution was sprayed all over the surface of the fine crystal seeds through the dual-channel air-blast nozzles to make new crystal seed and to make them grow up. The denigration reaction occurred when the internal temperature of the fluid-bed was kept at about 300 degree C by the outside and inside heat apparatus. The product were transported crossing the valve and spiral transfer to pack. The tail gas was purified and discharged. Through the fluid-bed's running, the variation discipline of temperature and the pressure, the effect curve of the quality of product accumulated to pressure drop were determined. At the same time, the gentrification temperature, the distributed heat and the transfer mode were tested. (authors)

Variable Denticity in Carboxylate Binding to the Uranyl Coordination Complexes

International Nuclear Information System (INIS)

Groenewold, G.S.; De Jong, Wibe A.; Oomens, Jos; Van Stipdonk, Michael J.

2010-01-01

Tris-carboxylate complexes of the uranyl (UO2)2+ cation with acetate and benzoate were generated using electrospray ionization mass spectrometry, and then isolated in a Fourier transformion cyclotron resonance mass spectrometer. Wavelength-selective infrared multiple photon dissociation (IRMPD) of the tris-acetatouranyl anion resulted in a redox elimination of an acetate radical, which was used to generate an IR spectrum that consisted of six prominent absorption bands. These were interpreted with the aid of density functional theory calculations in terms of symmetric and antisymmetric -CO2 stretches of both the monodentate and bidentate acetate, CH3 bending and umbrella vibrations, and a uranyl O-U-O asymmetric stretch. The comparison of the calculated and measured IR spectra indicated that the tris-acetate complex contained two acetate ligands bound in a bidentate fashion, while the third acetate was monodentate. In similar fashion, the tris-benzoate uranyl anion was formed and photodissociated by loss of a benzoate radical, enabling measurement of the infrared spectrum that was in close agreement with that calculated for a structure containing one monodentate, and two bidentate benzoate ligands.

Energy transfer and quenching processes of excited uranyl ion and lanthanide ions in solutions

International Nuclear Information System (INIS)

Yamamura, Tomoo; Tomiyasu, Hiroshi

1995-01-01

Deactivation processes of photoexcited uranyl ion by various lanthanide ions in aqueous solution were studied. Each lanthanide ions show different interaction with excited uranyl ion depending on its lowest excited energy level, the number of 4f electrons and the acid concentration of the solution. (author)

Growth of Cu(In,Al)(Se,S)2 thin films by selenization and sulfurization for a wide bandgap absorber

International Nuclear Information System (INIS)

Fujiwara, C.; Kawasaki, Y.; Sato, T.; Sugiyama, M.; Chichibu, S.F.

2010-01-01

Full text : Chalcopyrite structure Cu(In 1 .xAlx)(S y Se 1 -y) 2 (CIASS) alloys are attracting attention as promising candidates for the light-absorbing medium of high conversion efficiency, low cost, and lightweight solar cells. In addition, according to the wide variation in the bandgap energy (1.0-3.5eV), multiple-junction or tandem solar cells able to be fabricated using CIASS films of different compositions, x and y. In fact, several research groups have recently fabricated Cu(In,Al)Se 2 -based solar cells, and a high μ of 16.9 percent has been demonstrated. The sulfurization following selenization of Cu(In,Ga)Se2 (CIGS) films is believed to be promising for bandgap engineering of absorber material. Furthermore, it has been reported that the controlled incorporation of sulfur into CIGS films reduces the carrier recombination in the space charge region due to the deep trap states. Therefore, the sulfurization following selenization is expected to be used as a method of growth of CIASS films. However, sulfurization condition following selenization for obtaining CIASS films has not been clarified. The crystal growth of CIASS must be studied for solar cell applications. In this study, the advantages of using sulfurization for the growth of CIASS will be presented. Cu-In-Al precursors were selenized using diethylselenide (DESe) at 515-570 degrees Celsium for 60- 90 min under atmospheric pressure. The flow rates of DESe and N 2 carrier gases were 35 imol/min and 2 L/min, respectively. The films were then sulfurized at 550 degrees Celsium using S vapor. These films were characterized by SEM, EDX, XRD, and PL measurements. Using the selenization and sulfurization technique, polycrystalline Cu(In,Al)Se 2 , CuIn(Se,S) 2 , CuInS 2 films with thickness of approximately 2.0 im were formed without additional annealing. The films adhered well to the Mo/SLG substrate, which was confirmed by the peeling test. Phase separations, i.e. distinct peaks corresponding to CuInSe 2

Kinetic investigation of uranyl-uranophile complexation. 1. Macrocyclic kinetic effect and macrocyclic protection effect

International Nuclear Information System (INIS)

Tabushi, I.; Yoshizawa, A.

1986-01-01

Equilibria and rates of ligand-exchange reactions between uranyl tricarbonate and dithiocarbamates and between uranyl tris-(dithiocarbamates) and carbonate were studied under a variety of conditions. The dithiocarbamates used were acyclic diethyl-dithiocarbamate and macrocyclic tris(dithiocarbamate). The acyclic ligand showed a triphasic (successive three-step) equilibrium with three different equilibrium constants while the macrocyclic ligand showed a clear monophasic (one-step) equilibrium with a much larger stability constant for the dithiocarbamate-uranyl complex. The macrocyclic ligand showed the S/sub N/2-type ligand-exchange rate in the forward as well as reverse process, while the first step of the acyclic ligand-exchange reaction proceeded via the S/sub N/1-type mechanism. This kinetic macrocyclic effect on molecularity is interpreted as the result of a unique topological requirement of uranyl complexation. The macrocyclic ligand also exhibited a clear protection effect, leading to the large stability constant. 19 references, 10 figures, 2 tables

Water structure and aqueous uranyl(VI) adsorption equilibria onto external surfaces of beidellite, montmorillonite, and pyrophyllite: results from molecular simulations.

Science.gov (United States)

Greathouse, Jeffery A; Cygan, Randall T

2006-06-15

Molecular dynamics simulations were performed to provide a systematic study of aqueous uranyl adsorption onto the external surface of 2:1 dioctahedral clays. Our understanding of this key process is critical in predicting the fate of radioactive contaminants in natural groundwaters. These simulations provide atomistic detail to help explain experimental trends in uranyl adsorption onto natural media containing smectite clays. Aqueous uranyl concentrations ranged from 0.027 to 0.162 M. Sodium ions and carbonate ions (0.027-0.243 M) were also present in the aqueous regions to more faithfully model a stream of uranyl-containing groundwater contacting a mineral system comprised of Na-smectite. No adsorption occurred near the pyrophyllite surface, and there was little difference in uranyl adsorption onto the beidellite and montmorillonite, despite the difference in location of clay layer charge between the two. At low uranyl concentration, the pentaaquouranyl complex dominates in solution and readily adsorbs to the clay basal plane. At higher uranyl (and carbonate) concentrations, the mono(carbonato) complex forms in solution, and uranyl adsorption decreases. Sodium adsorption onto beidellite occurred both as inner- and outer-sphere surface complexes, again with little effect on uranyl adsorption. Uranyl surface complexes consisted primarily of the pentaaquo cation (85%) and to a lesser extent the mono(carbonato) species (15%). Speciation diagrams of the aqueous region indicate that the mono(carbonato)uranyl complex is abundant at high ionic strength. Oligomeric uranyl complexes are observed at high ionic strength, particularly near the pyrophyllite and montmorillonite surfaces. Atomic density profiles of water oxygen and hydrogen atoms are nearly identical near the beidellite and montmorillonite surfaces. Water structure therefore appears to be governed by the presence of adsorbed ions and not by the location of layer charge associated with the substrate. The water

Kinetic studies of uranyl ion adsorption on acrylonitrile (AN) / polyethylene glycol (PEG) interpenetrating networks (IPN)

International Nuclear Information System (INIS)

Aycik, G.A.; Gurellier, R.

2004-01-01

The kinetics of the adsorption of uranyl ions on amidoximated acrylonitrile (AN)/ polyethylene glycol (PEG) interpenetrating network (IPNs) from aqueous solutions was studied as a function of time and temperature. Adsorption analyses were performed for definite uranyl ion concentrations of 1x10 -2 M and at four different temperatures as 290K, 298K, 308K and 318K. Adsorption time was increased from zero to 48 hours. Adsorption capacities of uranyl ions by PEG/AN IPNS were determined by gamma spectrometer. The results indicate that adsorption capacity increases linearly with increasing temperature. The max adsorption capacity was found as 602 mgu/g IPN at 308K. Adsorption rate was evaluated from the curve plotted of adsorption capacity versus time, for each temperature. Rate constants for uranyl ions adsorption on amidoximated ipns were calculated for 290K, 298K, 308K and 318K at the solution concentration of 1x10 -2 M . The results showed that as the temperature increases the rate constant increases exponentially too. The mean activation energy of uranyl ions adsorption was found as 34.6 kJ/mole by using arrhenius equation. (author)

Precipitation characteristics of uranyl ions at different pHs depending on the presence of carbonate ions and hydrogen peroxide.

Science.gov (United States)

Kim, Kwang-Wook; Kim, Yeon-Hwa; Lee, Se-yoon; Lee, Jae-Won; Joe, Kih-Soo; Lee, Eil-Hee; Kim, Jong-Seung; Song, Kyuseok; Song, Kee-Chan

2009-04-01

This work studied the dissolution of uranium dioxide and precipitation characteristics of uranyl ions in alkaline and acidic solutions depending on the presence of carbonate ions and H2O2 in the solutions at different pHs controlled by adding HNO3 or NaOH in the solution. The chemical structures of the precipitates generated in different conditions were evaluated and compared by using XRD, SEM, TG-DT, and IR analyses together. The sizes and forms of the precipitates in the solutions were evaluated, as well. The uranyl ions were precipitated in the various forms, depending on the solution pH and the presences of hydrogen peroxide and carbonate ions in the solution. In a 0.5 M Na2CO3 solution with H2O2, where the uranyl ions formed mixed uranyl peroxy-carbonato complexes, the uranyl ions were precipitated as a uranium peroxide of UO4(H20)4 at pH 3-4, and precipitated as a clarkeite of Na2U2Ox(OH)y(H2O)z above pH 13. In the same carbonate solution without H2O2, where the uranyl ions formed uranyl tris-carbonato complex, the uranyl ions were observed to be precipitated as a different form of clarkeite above pH 13. The precipitate of uranyl ions in a nitrate solution without carbonate ions and H2O2 at a high pH were studied together to compare the precipitate forms in the carbonate solutions.

Preparation of SnSe thin films by encapsulated selenization

International Nuclear Information System (INIS)

Sabar D. Hutagalung; Samsudi Sakrani; Yussof Wahab

1994-01-01

Tin selenide thin films were prepared by encapsulated selenization. A stacked layer of evaporated Sn and Se films were annealed in a carbon block at temperatures 100 - 500 degree Celsius for 3 hours. X-ray analysis and SEM (Scanning electron) micrograph results showed that SnSe was initially formed at 150 degree Celsius with crystal size 30.0 nm and reached optimum formation at 200 daximum of 57.4 % yield of 5-decene. Other factors such as reaction temperatures, types of solvent and wt% of rhenium loadings influence the activity of the catalytic system

Contribution to the study of uranyl salts in butyl phosphate solutions

International Nuclear Information System (INIS)

Coulon, A.

1965-06-01

A spectroscopic study in the normal infrared region and involving the following associations: tri-alkyl phosphates (tri-butyl, tri-ethyl, tri-methyl), uranyl salts (nitrate, chloride, acetate) has confirmed the existence of an interaction between the phosphoryl group and the uranium atom, as shown by a movement of absorption band for the valency P = 0 from ∼ 1270 cm -1 to ∼ 1180 cm -1 . A study of the preparation, analysis and spectroscopy of the solids obtained by the precipitation of uranyl salts by acid butyl phosphates has been carried out. By infrared spectrophotometry it has been shown that the tri-butyl and di-butyl phosphates are associated in non-polar diluents even before the uranium is introduced. The extraction of uranyl salts from acid aqueous solutions by a diluted mixture of tri-butyl and di-butyl phosphates proceeds by different mechanisms according to the nature of the ion (nitrate or chloride). (author) [fr

Uranyl sorption onto alumina

International Nuclear Information System (INIS)

Jacobsson, A.M.M.

1997-01-01

The mechanism for the adsorption of uranyl onto alumina from aqueous solution was studied experimentally and the data were modeled using a triple layer surface complexation model. The experiments were carried out at low uranium concentrations (9 x 10 -11 --5 x 10 -8 M) in a CO 2 free environment at varying electrolyte concentrations (0.01--1 M) and pH (4.5--12). The first and second acid dissociation constants, pK a1 and pK a2 , of the alumina surface were determined from potentiometric titrations to be 7.2 ± 0.6 and 11.2 ± 0.4, respectively. The adsorption of uranium was found to be independent of the electrolyte concentration. The authors therefore conclude that the uranium binds as an inner sphere complex. The results were modeled using the code FITEQL. Two reactions of uranium with the surface were needed to fit the data, one forming a uranyl complex with a single surface hydroxyl and the other forming a bridged or bidentate complex reacting with two surface hydroxyls of the alumina. There was no evidence from these experiments of site heterogeneity. The constants used for the reactions were based in part on predictions made utilizing the Hard Soft Acid Base, HSAB, theory, relating the surface complexation constants to the hydrolysis of the sorbing metal ion and the acid dissociation constants of the mineral oxide surface

Sorptive fractionation of organic matter and formation of organo-hydroxy-aluminum complexes during litter biodegradation in the presence of gibbsite

Science.gov (United States)

K. Heckman; A.S. Grandy; X. Gao; M. Keiluweit; K. Wickings; K. Carpenter; J. Chorover; C. Rasmussen

2013-01-01

Solid and aqueous phase Al species are recognized to affect organic matter (OM) stabilization in forest soils. However, little is known about the dynamics of formation, composition and dissolution of organo-Al hydroxide complexes in microbially-active soil systems, where plant litter is subject to microbial decomposition in close proximity to mineral weathering...

Sorption mechanisms of selenium species (selenite and selenate) on copper-based minerals

International Nuclear Information System (INIS)

Devoy, J.

2001-09-01

The sorption of radionuclides on the surface of minerals represents a process capable to delay the migration of the elements from a spent fuel deep repository towards the biosphere. In the framework of a deep underground repository, an engineered clay barrier has a high trapping capacity for cationic radio-elements, in particular because of the negative charge of clay surfaces. However, anionic radioelements like selenium species, would be only weakly retained by chemical processes. In order to optimize the trapping capacity of a clay barrier with respect to anionic species, prospective studies are carried out in order to find and evaluate some minerals with specific chemical trapping functions. Among radionuclides, the case of selenium has to be considered because its isotope 79 Se is present in radioactive wastes and has a half life time of 6.5 10 4 years. It is also judicious to find a mineral capable of trapping simultaneously several anionic radio-elements. Copper oxides and sulfides (Cu 2 O, CuO, Cu 2 S, CuS, CuFeS 2 and Cu 5 FeS 4 ) are good adsorbents with respect to selenium species (selenite and selenate). These minerals, with their selenium retention properties, could be used also for the decontamination of soils and waters or to process industrial effluents. The sorption mechanisms have been studied in details for copper oxides (Cu 2 O and CuO) with respect to selenite and selenate. Chalcomenite precipitates in acid pH conditions when selenite is added to a Cu 2 O and CuO suspension. Selenate, in contact with cuprite (Cu 2 O) leads also to a selenium-based precipitate in acid pH environment. For higher pH values, selenite and selenate are adsorbed on copper oxides (Cu 2 O and CuO) and lead to internal and external sphere complexes, respectively. In the case of a selenite/cuprite mixture in basic pH environment and at the equilibrium, a chemical reaction occurs between the oxidation product of cuprite, Cu(OH) 2 and HSeO 3 . A preliminary study of

Organo-bridged silsesquioxane titanates for heterogeneous catalytic epoxidation with aqueous hydrogen peroxide

NARCIS (Netherlands)

Wang, Y.M.; Magusin, P.C.M.M.; Santen, van R.A.; Abbenhuis, H.C.L.

2007-01-01

Organo-bridged silsesquioxane titanates for heterogeneous catalytic epoxidation with aqueous hydrogen peroxide were synthesized through the acid-catalyzed hydrolysis and co-condensation of organotrialkoxysilane monomers and a,¿-bis(trialkoxysilyl) alkane cross-linkers in ethanol–water solution, with

Preparation, solubility, infrared spectra and radiolysis of tetramethylammonium hydrogenselenate monohydrate and lithium tetramethylammonium selenate tetrahydrate

Czech Academy of Sciences Publication Activity Database

Havlíček, D.; Turek, L.; Plocek, Jiří; Mička, Z.

2006-01-01

Roč. 71, č. 3 (2006), s. 411-422 ISSN 0010-0765 Institutional research plan: CEZ:AV0Z40320502 Keywords : tetramethylammonium salts * hydrogenselenates * selenates Subject RIV: CA - Inorganic Chemistry Impact factor: 0.881, year: 2006

Expanding the Library of Uranyl Amide Derivatives: New Complexes Featuring the tert-Butyldimethylsilylamide Ligand.

Science.gov (United States)

Pattenaude, Scott A; Coughlin, Ezra J; Collins, Tyler S; Zeller, Matthias; Bart, Suzanne C

2018-04-16

New uranyl derivatives featuring the amide ligand, -N(SiHMe 2 ) t Bu, were synthesized and characterized by X-ray crystallography, multinuclear NMR spectroscopy, and absorption spectroscopies. Steric properties of these complexes were also quantified using the computational program Solid-G. The increased basicity of the free ligand -N(SiHMe 2 ) t Bu was demonstrated by direct comparison to -N(SiMe 3 ) 2 , a popular supporting ligand for uranyl. Substitutional lability on a uranyl center was also demonstrated by exchange with the -N(SiMe 3 ) 2 ligand. The increased basicity of this ligand and diverse characterization handles discussed here will make these compounds useful synthons for future reactivity.

Design of one evaporation system for uranyl nitrate solution

International Nuclear Information System (INIS)

Mancilla Romero, R.J.

1975-01-01

The authors propose an instant evaporation system with recirculation of the concentrated solution to raise the concentration from 50 to 1500 g of uranium per litre of solution. The capacity of the plant is to be 14.1 kg of uranium per hour. The main equipment used in the system is as follows: 1. Ring-type heat exchanger, for increasing the temperature of the mixture of fresh and recirculated solution from 80 to 115 0 C; 2. Separation tank, in which instant evaporation is carried out. The absolute pressure inside the tank will be 500 mmHg, with steam separation from a concentrated (78.5 wt.%) uranyl nitrate solution; 3. Desuperheater-condenser of horizontal tubular type for condensing water vapour and recovering any uranyl nitrate that may have been entrained; 4. Storage tank for the concentrate, with a capacity for one day's normal operation, and a heating coil to prevent crystallization of the concentrated solution; 5. Two storage tanks for feed and condensate with capacity for one day's normal operation; 6. Supporting structure for the above components. Virtually all equipment in contact with the uranyl nitrate solution will be made of 304 stainless steel. Saturated steam at 143.3 0 C will be required. The cost of the proposed system is $543 030.00. (author)

Uranyl sensor based on a N,N?-bis(salicylidene)-2-hydroxy-phenylmethanediamine and multiwall carbon nanotube electrode

International Nuclear Information System (INIS)

Sayed Mehdi Ghoreishi; Mohsen Behpour; Samaneh Mazaheri; Hossein Naeimi

2012-01-01

The electrochemical determination of uranyl was investigated by using carbon paste electrode modified with a Schiff base namely N,N'-bis(salicylidene)-2-hydroxy-phenylmethanediamine (SHPMD/CPE) and also in the presence of carbon nanotube (SHPMD/CNT/CPE). The both modified electrodes displayed an irreversible peak at E pa = 0.798 V versus Ag/AgCl. The electrocatalytic reduction of uranyl has been studied on SHPMD/CNT/CPE, using cyclic and differential pulse voltammetry, chronocoulometry and linear sweep techniques. Electrochemical parameters including the diffusion coefficient (D), the electron transfer coefficient (α), the ionic exchange current (i) and the redox reaction rate constant (K) were determined for the reduction of uranyl on the surface of the modified electrodes. Linear range concentration is 0.002-0.6 μmol L -1 and the detection limit of uranyl is 0.206 nmol L -1 . The proposed method was used to detect uranyl in natural waters and good recovery was achieved. (author)

Uptake and speciation of selenium in garlic cultivated in soil amended with symbiotic fungi (mycorrhiza) and selenate

Energy Technology Data Exchange (ETDEWEB)

Larsen, Erik H.; Hansen, Marianne; Rasmussen, Peter Have; Sloth, Jens J. [Danish Institute for Food and Veterinary Research, Department of Food Chemistry, Soeborg (Denmark); Lobinski, Ryszard; Ruzik, Rafal; Mazurowska, Lena [CNRS UMR 5034, Pau (France); Warsaw University of Technology, Department of Analytical Chemistry, Warsaw (Poland); Burger-Meyer, Karin; Scholten, Olga [Wageningen University and Research Centre, Plant Research International (PRI), P.O. Box 16, Wageningen (Netherlands); Kik, Chris [Wageningen University and Research Centre, Plant Research International (PRI), P.O. Box 16, Wageningen (Netherlands); Wageningen University and Research Centre, Centre for Genetic Resources, The Netherlands (CGN), P.O. Box 16, Wageningen (Netherlands)

2006-07-15

The scope of the work was to investigate the influence of selenate fertilisation and the addition of symbiotic fungi (mycorrhiza) to soil on selenium and selenium species concentrations in garlic. The selenium species were extracted from garlic cultivated in experimental plots by proteolytic enzymes, which ensured liberation of selenium species contained in peptides or proteins. Separate extractions using an aqueous solution of enzyme-deactivating hydroxylamine hydrochloride counteracted the possible degradation of labile selenium species by enzymes (such as alliinase) that occur naturally in garlic. The selenium content in garlic, which was analysed by ICP-MS, showed that addition of mycorrhiza to the natural soil increased the selenium uptake by garlic tenfold to 15 {mu}g g{sup -1} (dry mass). Fertilisation with selenate and addition of mycorrhiza strongly increased the selenium content in garlic to around one part per thousand. The parallel analysis of the sample extracts by cation exchange and reversed-phase HPLC with ICP-MS detection showed that {gamma}-glutamyl-Se-methyl-selenocysteine amounted to 2/3, whereas methylselenocysteine, selenomethionine and selenate each amounted to a few percent of the total chromatographed selenium in all garlic samples. Se-allyl-selenocysteine and Se-propyl-selenocysteine, which are selenium analogues of biologically active sulfur-containing amino acids known to occur in garlic, were searched for but not detected in any of the extracts. The amendment of soil by mycorrhiza and/or by selenate increased the content of selenium but not the distribution of detected selenium species in garlic. Finally, the use of two-dimensional HPLC (size exclusion followed by reversed-phase) allowed the structural characterisation of {gamma}-glutamyl-Se-methyl-selenocysteine and {gamma}-glutamyl-Se-methyl-selenomethionine in isolated chromatographic fractions by quadrupole time-of-flight mass spectrometry. (orig.)

Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms.

Science.gov (United States)

Carter, Korey P; Kalaj, Mark; Surbella, Robert G; Ducati, Lucas C; Autschbach, Jochen; Cahill, Christopher L

2017-11-02

Engaging the nominally terminal oxo atoms of the linear uranyl (UO 2 2+ ) cation in non-covalent interactions represents both a significant challenge and opportunity within the field of actinide hybrid materials. An approach has been developed for promoting oxo atom participation in a range of non-covalent interactions, through judicious choice of electron donating equatorial ligands and appropriately polarizable halogen-donor atoms. As such, a family of uranyl hybrid materials was generated based on a combination of 2,5-dihalobenzoic acid and aromatic, chelating N-donor ligands. Delineation of criteria for oxo participation in halogen bonding interactions has been achieved by preparing materials containing 2,5-dichloro- (25diClBA) and 2,5-dibromobenzoic acid (25diBrBA) coupled with 2,2'-bipyridine (bipy) (1 and 2), 1,10-phenanthroline (phen) (3-5), 2,2':6',2''-terpyridine (terpy) (6-8), or 4'-chloro-2,2':6',2''-terpyridine (Cl-terpy) (9-10), which have been characterized through single crystal X-ray diffraction, Raman, Infrared (IR), and luminescence spectroscopy, as well as through density functional calculations of electrostatic potentials. Looking comprehensively, these results are compared with recently published analogues featuring 2,5-diiodobenzoic acid which indicate that although inclusion of a capping ligand in the uranyl first coordination sphere is important, it is the polarizability of the selected halogen atom that ultimately drives halogen bonding interactions with the uranyl oxo atoms. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

VOLATILE ORGANO-METALLOIDS IN BIO-SOLID MATERIALS: ANALYSIS BY VACUUM DISTILLATION-GC/MS

Science.gov (United States)

An analytical method based on vacuum distillation-gas chromatography-mass spectrometry (VD-GC-MS)was developed for determining volatile organo-metalloid contaminants in bio-solid materials. Methodperformance was evaluated for dimethylselenide (DMSe), dimethyldisel...

Isolation of a star-shaped uranium(V/VI) cluster from the anaerobic photochemical reduction of uranyl(VI)

Energy Technology Data Exchange (ETDEWEB)

Chatelain, Lucile; White, Sarah; Scopelliti, Rosario; Mazzanti, Marinella [Ecole Polytechnique Federale de Lausanne (EPFL) (Switzerland). Inst. de Sciences et Ingenierie Chimiques

2016-11-07

Actinide oxo clusters are an important class of compounds due to their impact on actinide migration in the environment. The photolytic reduction of uranyl(VI) has potential application in catalysis and spent nuclear fuel reprocessing, but the intermediate species involved in this reduction have not yet been elucidated. Here we show that the photolysis of partially hydrated uranyl(VI) in anaerobic conditions leads to the reduction of uranyl(VI), and to the incorporation of the resulting U{sup V} species into the stable mixed-valent star-shaped U{sup VI}/U{sup V} oxo cluster [U(UO{sub 2}){sub 5}(μ{sub 3}-O){sub 5}(PhCOO){sub 5}(Py){sub 7}]. This cluster is only the second example of a U{sup VI}/U{sup V} cluster and the first one associating uranyl groups to a non-uranyl(V) center. The U{sup V} center in 1 is stable, while the reaction of uranyl(V) iodide with potassium benzoate leads to immediate disproportionation and formation of the U{sub 12}{sup IV}U{sub 4}{sup V}O{sub 24} cluster {[K(Py)_2]_2[K(Py)]_2[U_1_6O_2_4(PhCOO)_2_4(Py)_2]}.

Safe use and waste disposal of uranyl acetate

International Nuclear Information System (INIS)

Sanchez, A.; Calvo, S.; Caparros, G.; Gallego, E.; Rascon, J.; Valladares, M.C.

2006-01-01

Radioactive labelled molecules are widely used in Biological Research Centres. The most common radioisotopes are: 32 P, 33 P, 35 S, 3 H, 14 C, 125 I and 45 Ca.Due to the inherent risk in the manipulation of these radiation unsealed sources, in these radioactive installations there are established radiological protection programs to reduce this potential risk and the professional exposure in the manipulation and in the radioactive waste generated. In these Biological Research Centres we used techniques with other radioactive products less used, that we must to control. It is the case of the use of uranyl acetate. Uranyl acetate is a uranium salt used in the preparation of samples for analysis in the electron microscope. Although the amounts used are relatively small, both the chemical and radiological toxicities of these compounds are significant and require working whit that some cautions, with the main emphasis on avoiding the possibility of inhalation of fine particulates or vapours. Due to changes in the Spanish regulations for this product, it was necessary to establish a specific control program in its manipulation. The purpose of this work is the accomplishment of specific protocols for the acquisition, manipulation, contamination measurements, inspections of the work zone and waste management, in order to minimize the risks in the manipulation of uranyl acetate,as well as apply the knowledge and use of specific norms for working with this product. (authors)

Safe use and waste disposal of uranyl acetate

Energy Technology Data Exchange (ETDEWEB)

Sanchez, A.; Calvo, S.; Caparros, G.; Gallego, E.; Rascon, J.; Valladares, M.C. [Centro de Biologia Molecular, Madrid (Spain)

2006-07-01

Radioactive labelled molecules are widely used in Biological Research Centres. The most common radioisotopes are: {sup 32}P,{sup 33}P, {sup 35}S,{sup 3}H,{sup 14}C,{sup 125}I and {sup 45}Ca.Due to the inherent risk in the manipulation of these radiation unsealed sources, in these radioactive installations there are established radiological protection programs to reduce this potential risk and the professional exposure in the manipulation and in the radioactive waste generated. In these Biological Research Centres we used techniques with other radioactive products less used, that we must to control. It is the case of the use of uranyl acetate. Uranyl acetate is a uranium salt used in the preparation of samples for analysis in the electron microscope. Although the amounts used are relatively small, both the chemical and radiological toxicities of these compounds are significant and require working whit that some cautions, with the main emphasis on avoiding the possibility of inhalation of fine particulates or vapours. Due to changes in the Spanish regulations for this product, it was necessary to establish a specific control program in its manipulation. The purpose of this work is the accomplishment of specific protocols for the acquisition, manipulation, contamination measurements, inspections of the work zone and waste management, in order to minimize the risks in the manipulation of uranyl acetate,as well as apply the knowledge and use of specific norms for working with this product. (authors)

Corrosion evaluation of uranyl nitrate solution evaporator and denitrator in Tokai reprocessing plant

International Nuclear Information System (INIS)

Yamanaka, Atsushi; Hashimoto, Kowa; Uchida, Toyomi; Shirato, Yoji; Isozaki, Toshihiko; Nakamura, Yoshinobu

2011-01-01

The Tokai reprocessing plant (TRP) adopted the PUREX method in 1977 and has reprocessed spent nuclear fuel of 1140 tHM (tons of heavy metals) since then. The reprocessing equipment suffers from various corrosion phenomena because of high nitric acidity, solution ion concentrations, such as uranium, plutonium, and fission products, and temperature. Therefore, considering corrosion performance in such a severe environment, stainless steels, titanium steel, and so forth were employed as corrosion resistant materials. The severity of the corrosive environment depends on the nitric acid concentration and the temperature of the solution, and uranium in the solution reportedly does not significantly affect the corrosion of stainless steels and controls the corrosion rates of titanium steel. The TRP equipment that handles uranyl nitrate solution operates at a low nitric acid concentration and has not experienced corrosion problems until now. However, there is a report that corrosion rates of some stainless steels increase in proportion to rising uranium concentrations. The equipment that handles the uranyl nitrate solution in the TRP includes the evaporators, which concentrate uranyl nitrate to a maximum concentration of about 1000 gU/L (grams of uranium per liter), and the denitrator, where uranyl nitrate is converted to UO 3 powder at about 320degC. These equipments are therefore required to grasp the degree of the progress of corrosion to handle high-temperature and high-concentration uranyl nitrate. The evaluation of this equipment on the basis of thickness measurement confirmed only minor corrosion and indicated that the equipment would be fully adequate for future operation. (author)

Fabrication of Up-Conversion Phosphor Films on Flexible Substrates Using a Nanostructured Organo-Silicon.

Science.gov (United States)

Jeon, Young-Sun; Kim, Tae-Un; Kim, Seon-Hoon; Lee, Young-Hwan; Choi, Pil-Son; Hwang, Kyu-Seog

2018-03-01

Up-conversion phosphors have attracted considerable attention because of their applications in solid-state lasers, optical communications, flat-panel displays, photovoltaic cells, and biological labels. Among them, NaYF4 is reported as one of the most efficient hosts for infrared to visible photon up-conversion of Yb3+ and Er3+ ions. However, a low-temperature method is required for industrial scale fabrication of photonic and optoelectronic devices on flexible organic substrates. In this study, hexagonal β-NaYF4: 3 mol% Yb3+, 3 mol% Er3+ up-conversion phosphor using Ca2+ was prepared by chemical solution method. Then, we synthesized a nanostructured organo-silicon compound from methyl tri-methoxysilane and 3-glycidoxy-propyl-trimethoxy-silane. The transmittance of the organo-silicon compound was found to be over 90% in the wavelength range of 400~1500 nm. Then we prepared a fluoride-based phosphor paste by mixing the organo-silicon compound with Na(Ca)YF4:Yb3+, Er3+. Subsequently, this paste was coated on polyethylene terephthalate, followed by heat-treatment at 120 °C. The visible emission of the infrared detection card was found to be at 655 nm and 661 nm an excitation wavelength of 980 nm.

Selectivity in ligand binding to uranyl compounds: A synthetic, structural, thermodynamic and computational study

Energy Technology Data Exchange (ETDEWEB)

Arnold, John [Univ. of California, Berkeley, CA (United States)

2015-01-21

The uranyl cation (UO₂²⁺) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. It is anticipated that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials. The focus of this study is to synthesize uranyl complexes incorporating amidinate and guanidinate ligands. Both synthetic and computational methods are used to investigate novel equatorial ligand coordination and how this affects the basicity of the oxo ligands. Such an understanding will later apply to designing ligands incorporating functionalities that can bind uranyl both equatorially and axially for highly selective sequestration. Efficient and durable chromatography supports for lanthanide separation will be generated by (1) identifying robust peptoid-based ligands capable of binding different lanthanides with variable affinities, and (2) developing practical synthetic methods for the attachment of these ligands to Dowex ion exchange resins.

Selectivity in ligand binding to uranyl compounds: A synthetic, structural, thermodynamic and computational study

International Nuclear Information System (INIS)

Arnold, John

2015-01-01

The uranyl cation (UO 2 2+ ) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. It is anticipated that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials. The focus of this study is to synthesize uranyl complexes incorporating amidinate and guanidinate ligands. Both synthetic and computational methods are used to investigate novel equatorial ligand coordination and how this affects the basicity of the oxo ligands. Such an understanding will later apply to designing ligands incorporating functionalities that can bind uranyl both equatorially and axially for highly selective sequestration. Efficient and durable chromatography supports for lanthanide separation will be generated by (1) identifying robust peptoid-based ligands capable of binding different lanthanides with variable affinities, and (2) developing practical synthetic methods for the attachment of these ligands to Dowex ion exchange resins.

Photochemistry and exciplex of the uranyl ion in aqueous solution

International Nuclear Information System (INIS)

Marcantonatos, M.D.

1980-01-01

The effects of acidity, temperature, self-quenching and H-donor concentration on the luminescent state of the aqua-uranyl(VI) ion have been studied in aqueous acidic nitrate and perchlorate solution. The detailed results cannot be explained by any single simple mechanism such as radiative, non-radiative or spontaneous collisional quenching, or irreversible hydrogen abstraction from water. Quantitative analysis of the results shows a far more complex mechanism, involving the adiabatic formation of the species *UO 2 H 2+ and *U 2 O 4 H 4+ , as already proposed by the author. This mechanism is supported by state and m.o. correlations. The abstraction of hydrogen from water is shown to take place by H atom transfer in a *uranyl-water complex intermediate, rather than by attack of H + on the fully occupied πsub(u) orbitals of uranium(V) in a well-defined uranyl water complex with strong charge transfer character. A qualitative description of the exciplex *U 2 O 4 H 4+ is shown to be possible in a v.b. formalism and the origin of its radiative properties is discussed on this basis. (author)

Production of U3O8 by uranyl formate precipitation and calcination in a full-scale pilot facility

International Nuclear Information System (INIS)

Kendrick, L.S.; Wilson, W.A.; Mosley, W.C.

1984-08-01

The uranyl formate process for the production of U 3 O 8 with a controlled particle size has been extensively studied on a laboratory scale. Based on this study, a pilot-scale facility (the Uranyl Formate Facility) was built to investigate the key steps of the process on a larger scale. These steps were the precipitation of a uranyl formate monohydrate salt and the calcination of this salt to U 3 O 8 . Tests of the facility and process were conducted at conditions recommended by the laboratory-scale studies for a full-scale production facility. These tests demonstrated that U 3 O 8 of the required particle size for the PM process can be produced on a plant scale by the calcination of uranyl formate crystals. The performance of the U 3 O 8 produced by the uranyl formate process in fuel tube fabrication was also investigated. Small-scale extrusion tests of U 3 O 8 -Al cores which used the U 3 O 8 produced in the Uranyl Formate Facility were conducted. These tests demonstrated that the U 3 O 8 quality was satisfactory for the PM process

Determination of the stability of the uranyl ion sipped in τ-hydrogen phosphate of zirconium in sodic form

International Nuclear Information System (INIS)

Ordonez R, E.; Fernandez V, S.M.; Drot, R.; Simoni, E.

2005-01-01

The stability of the uranyl sipped in the zirconium τ-hydrogen phosphate in sodic form (τ-NaZrP), was carried out characterizing the complexes formed by Laser spectroscopy in the visible region and by X-ray photoelectron spectroscopy. The material was prepared by a new synthesis technique working in nitrogen atmosphere and to low temperatures. The sorption of the uranyl ion was made in acid media with concentrations of 10 -4 and 10 -5 of uranyl nitrate and with ion forces of 0.1 and 0.5 M of NaClO 4 . The spectra of induced fluorescence with laser (TRLFS) show that the uranyl is fixed in very acid media in three well differentiated species, to pH less acid, the specie of long half life disappears and are only those of short half life. The results of the binding energy obtained by XPS indicate that the binding energy of the uranyl confer it a stable character to the complex formed in the τ-NaZP, that makes to this material appropriate to retain to the uranyl in solution to high ion forces and in acid media. (Author)

Uranyl oxo activation and functionalization by metal cation coordination

International Nuclear Information System (INIS)

Arnold Polly, L.; Pecharman, A. F.; Hollis, E.; Parsons, S.; Love, J. B.; Yahia, A.; Maron, L.; Yahia, A.; Maron, L.

2010-01-01

The oxo groups in the uranyl ion [UO 2 ] 2+ - one of many oxo cations formed by metals from across the periodic table - are particularly inert, which explains the dominance of this ion in the laboratory and its persistence as an environmental contaminant. In contrast, transition metal oxo (M=O) compounds can be highly reactive and carry out difficult reactions such as the oxygenation of hydrocarbons. Here we show how the sequential addition of a lithium metal base to the uranyl ion constrained in a 'Pacman' environment results in lithium coordination to the U=O bonds and single-electron reduction. This reaction depends on the nature and stoichiometry of the lithium reagent and suggests that competing reduction and C-H bond activation reactions are occurring. (authors)

Treatment of uranyl nitrate and flouride solutions

International Nuclear Information System (INIS)

Rodrigo Otero, A.; Rodrigo Vilaseca, F.; Morales Calvo, G.

1977-01-01

A theoretical study on the fluoride complexes contained in uranyl and aluminium solutions has been carried out. Likewise concentration limits and Duhring diagrams for those solutions have been experimentally established. As a result, the optimum operation conditions for concentration by evaporation in the treatment plant, have been deduced. (Author) 12 refs

Crystallization of paraffins, formation of organo gels and flow in pipelines; Cristalizacao de parafinas, formacao de organogeis e escoamento em oleodutos

Energy Technology Data Exchange (ETDEWEB)

Vaz, Juliana Correia Bergallo; Mohamed, Rahoma Sadeg; Oliveira, Marcelo Ganzarolli de [Universidade Estadual de Campinas (UNICAMP), SP (Brazil)]. E-mails: jcbvaz8@hotmail.com; mohamed@feq.unicamp.br; mgo@iqm.unicamp.br

2003-06-01

In this work, polarized light microscopy , differential scan calorimetry, X-ray diffraction and viscosimetry were used to investigate the phase behavior of binary and tertiary mixtures of the paraffins C10 , C21 , C25 , C28 , C32 ,C36 and C40. Phase transition temperatures for the binary mixtures C28/C40 , C21/C40 , C28/C32 and C21/C25 were obtained using DSC measurements. The formation of organogels in C10/C21, C10/C28, C10/C36, C10/C40, C10/C21/C28, C10/C21/C40 and C10/C28/C40 mixtures was confirmed using other techniques. The evidence of the formation of organo gels systems allows phase diagrams to be interpreted from a new perspective that takes into account the important role of these systems in the transportation of oil in pipelines and its implications in the retention of large amounts of oil in the gel structure. The results obtained suggest that all paraffins mixtures, considered in this work, are potentially capable of forming organo gels at a given temperature and composition, except those that form solid solutions. A very important characteristic of organo gels is that they do not form under shear rate. Therefore, a turbulent oil flow would make it more difficult to form paraffinic organo gels. On the other hand, once they have been formed, organo gels do not get unstructured under shear and constant oscillation and with the increase of temperature, which could make it difficult for oil to flow . Thus, the characterization of the formation of these organo gels can provide new information to solve technological problems of oil flow. (author)

The treatment of uranyl nitrate from the AMOR process for VKTA Rossendorf

International Nuclear Information System (INIS)

Boessert, W.; Krempl, R.; Miller, J.W.

2003-01-01

The blending of uranyl nitrate solutions at VKTA and its subsequent treatment at BNFL-Sellafield is a significant step towards the safe and effective treatment of these enriched uranyl nitrate solutions. Overall the integration of the expertise of the international company BNFL/Westinghouse will lead to the achievement of a successful solution. This success has involved the integration of the project management and operational facilities of BNFL Sellafield with the local planning, design and manufacture capacities of Westinghouse Reaktor GmbH. (orig.)

Reactive transport of uranyl: fixation mode on silica and goethite; experiments in columns and closed reactors; simulations

International Nuclear Information System (INIS)

Gabriel, U.

1998-01-01

Uranium contaminated areas are found in mine waste disposal sites, former military areas, etc. The present study focuses on the identification or mechanisms which may lead contaminated soils to become a sudden potential threat to surface and ground waters. Mechanisms were studied on model material at two levels. On the molecular scale, the complexation of uranyl at trace metal concentrations was investigated with amorphous silica. Complexation is shown to occur via the formation of surface complexes, characterised by different time-resolved laser-induced luminescence spectra and life times and stoichiometry. On the macro-scale the transport behaviour of uranyl in a cristobalite-goethite-carbonate-uranyl system was investigated with laboratory column and batch experiments. Uranium mobility was found to be controlled by the interaction between physical transport and a reversible, rate-controlled, fixation reaction. Sorption was shown to be an ensemble of competing solution and surface complexation reactions, leading to an apparent non-linear (Langmuir-like) adsorption isotherm. Finally the impact of a sudden change in background geochemistry was studied. Conditions leading to a dramatic mobilization of uranium from mildly contaminated systems were experimentally identified. Maximal uranyl concentration are controlled by the total extractable uranyl in the system and limited by uranyl solubility. Evolution of the background geochemical conditions is thus an important part of contaminated sites risk assessment. (author)

Stabilization of heavy metals in soil using two organo-bentonites.

Science.gov (United States)

Yu, Kai; Xu, Jian; Jiang, Xiaohong; Liu, Cun; McCall, Wesley; Lu, Jinlong

2017-10-01

Stabilization of Cu, Zn, Cd, Hg, Cr and As in soil using tetramethylammonium (TMA) and dodecyltrimethylammonium (DTMA) modified bentonites (T-Bents and D-Bents) as amendments was investigated. Toxicity characteristic leaching procedure (TCLP) was used to quantify the metal mobility after soil treatment. The structural parameters of modified bentonites, including the BET surface area, basal spacing and zeta potential were obtained as a function of the TMA and DTMA loading at 40, 80, 120, 160 and 200% of the bentonite's cation exchange capacity, respectively. The results indicated that the characteristics of the organo-bentonites fundamentally varied depending on the species and concentration of modifiers loaded on bentonite. T-Bents and D-Bents manifested distinct immobilization effectiveness towards various metals. In association with the organo-bentonite characteristics, the main interactive mechanisms for Cu, Zn and Cd proceeded via cation exchange, Hg proceeded via physical adsorption and partitioning, Cr and As proceeded via specific adsorption and electrostatic attraction, respectively. This study provided operational and mechanistic basis for optimizing the organic clay synthesis and selecting as the appropriate amendment for remediation of heavy metal contaminated soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

Investigation of uranyl phosphite interaction with some amides

International Nuclear Information System (INIS)

Avduevskaya, K.A.; Ragulina, N.B.; Rozanov, I.A.; Mukhajlov, Yu.N.; Kanishcheva, A.S.; Grevtseva, T.G.

1981-01-01

Uranyl (amide) phosphitocomplexes of [UO 2 HPO 3 H 2 OAA]xH 2 O, [UO 2 HPO 3 (AA) 2 ], [UO 2 HPO 3 H 2 O DMC], [UO 2 HPO 3 H 2 ODMFA], [UO 2 HPO 3 DAMA] and UO 2 HPO 3 x2FAxH 2 O compositions, where AA-acetamide; DMC-N, N-dimetyl carbamide, DMFA-dimetyl formamide; DAMA-diamide of malonic acid; FA-formamide, are separated, identified and investigated. Derivatives of mono substituted uranyl phosphite of UO 2 (H 2 PO 3 ) 2 x2FA and [UO 2 (H 2 PO 3 ) 2 H 2 O]x2TMC composition (where TMC-tetramethyl carbamide), are synthesized. Structures of complexes with DAMA, TMC, DMFA and acid dimethyl-ammonium diphosphitouranylate-(CH 3 ] 2 NH 2 x[UO 2 (HPO 3 ) 3 (H 2 PO 3 )] are investigated [ru

Investigation of uranyl nitrate complexes with trialkylphosphine oxides

International Nuclear Information System (INIS)

Kobets, L.V.; Kopashova, I.M.; Dik, T.A.; Volodin, I.A.; Kovalenko, M.A.; Semenij, V.Ya.

1982-01-01

Using the methods of vibrational spectroscopy and thermal analysis a number of uranyl complexes with trialkylphosphine oxides of the general formula UO 2 (NO 3 ) 2 x2R 3 PO, where R-C 2 H 5 -C 10 H 21 have been studied. Infrared and Raman spectra are interpreted according to vibration types. Comparison of vibrational spectra of the complexes in solid phase and solutions of organic solvents permitted to find the differences in position and amount of acids responsible for complexing. It is detected that in the series of complexes investigated the strength of uranyl bond with phosphoryl group oxygen practically remains stable, whereas degree of covalence of nitrate groups is observed. The pointed out peculiarities are interpreted proceeding from the presence of bridge nitrate groups in the structure of the complexes. Thermal stability of the complexes is studied, chemism of their decomposition being suggested

Organo chlorine pesticides (OCPs) contaminants in sediments from Karachi harbour, Pakistan

International Nuclear Information System (INIS)

Khan, N.; Khan, S.H.; Amjad, S.; Muller, J.; Nizamani, S.; Bhanger, M.I.

2010-01-01

Mangrove swamps, inter tidal mud flats and creeks of backwaters represent main feature of Karachi harbour area. Karachi harbour sediment is under continuous influence of untreated industrial effluents and domestic waste discharged into the Harbour area via Lyari River. Sediment samples from sixteen locations were collected to evaluate the levels of contamination of organo chlorine pesticides (OCPs) in Karachi harbour and adjoining areas. It has been observed that residual concentrations of various organo chlorine pesticides were considerably higher in the semi-enclosed area of the upper Harbour in the vicinity of the discharge point of Lyari River. The residue of DDT mainly its metabolites (DDE and DDD) were widely distributed and have been detected in most of the sediment samples in relatively higher concentrations as compared to other OCPs. The higher levels of the DDTs would attribute to low tidal flushing of the area. The high proportion of pp'-DDE in the most sediment sampled (41-95%) suggested old inputs of DDTs in the environment. Ratio of sigma DDT and DDT was in the range of 0.04 - 0.24 at all locations which also reflects that the discharges of DDT were negligible in the Harbour area. This may be due to the restrictions being implemented on the use of DDTs and Pakistan has also switched over to natural pest control or using safer formulas. The data obtained during the study showed that concentration levels of other pesticides such as HCHs, HCB and Cyclodienes in the sediment were generally lower than the threshold levels known to harm wildlife by OCPs. The results clearly indicate that elevated concentration of organo chlorine pesticides (OCPs) in the marine sediment of Karachi harbour and adjoining area was localized and much lower than the concentrations reported from neighbouring and regional countries which suggests/confirms that the present use of pesticide in Pakistan is environmentally safe. (author)

Dependency of Nanodiamond Particle Size and Outermost-Surface Composition on Organo-Modification: Evaluation by Formation of Organized Molecular Films and Nanohybridization with Organic Polymers.

Science.gov (United States)

Tasaki, Taira; Guo, Yifei; Meng, Qi; Mamun, Muhammad Abdullah Al; Kasahara, Yusuke; Akasaka, Shuichi; Fujimori, Atsuhiro

2017-04-26

The formation behavior of organized organo-modified nanodiamond films and polymer nanocomposites has been investigated using nanodiamonds of several different particle sizes and outermost-surface compositions. The nanodiamond particle sizes used in this study were 3 and 5 nm, and the outermost surface contained -OH and/or -COOH groups. The nanodiamond was organo-modified to prepare -OH 2 + cations and -COO - anions on the outermost surface by carboxylic anion of fatty acid and long-chain phosphonium cation, respectively. The surface of nanodiamond is known to be covered with a nanolayer of adsorbed water, which was exploited here for the organo-modification of nanodiamond with long-chain fatty acids via adsorption, leading to nanodispersions of nanodiamond in general organic solvents as a mimic of solvency. Particle multilayers were then formed via the Langmuir-Blodgett technique and subjected to fine structural analysis. The organo-modification enabled integration and multilayer formation of inorganic nanoparticles due to enhancement of the van der Waals interactions between the chains. Therefore, "encounters" between the organo-modifying chain and the inorganic particles led to solubilization of the inorganic particles and enhanced interactions between the particles; this can be regarded as imparting a new functionality to the organic molecules. Nanocomposites with a transparent crystalline polymer were fabricated by nanodispersing the nanodiamond into the polymer matrix, which was achievable due to the organo-modification. The resulting transparent nanocomposites displayed enhanced degrees of crystallization and improved crystallization temperatures, compared with the neat polymer, due to a nucleation effect.

Controlled formation of MoSe{sub 2} by MoN{sub x} thin film as a diffusion barrier against Se during selenization annealing for CIGS solar cell

Energy Technology Data Exchange (ETDEWEB)

Jeon, Chan-Wook [School of Chemical Engineering, Yeungnam University, Gyeongsangbuk-do 712-749 (Korea, Republic of); Cheon, Taehoon [School of Materials Science and Engineering, Yeungnam University, Gyeongsangbuk-do 712-749 (Korea, Republic of); Center for Core Research Facilities, DaeguGyeongbuk Institute of Science & Technology, Daegu (Korea, Republic of); Kim, Hangil [School of Materials Science and Engineering, Yeungnam University, Gyeongsangbuk-do 712-749 (Korea, Republic of); Kwon, Min-Su [School of Chemical Engineering, Yeungnam University, Gyeongsangbuk-do 712-749 (Korea, Republic of); Kim, Soo-Hyun [School of Materials Science and Engineering, Yeungnam University, Gyeongsangbuk-do 712-749 (Korea, Republic of)

2015-09-25

Highlights: • Mo/MoN{sub x}/Mo multilayer was investigated as a back contact for CIGS solar cell. • The MoN{sub x} protected the underlying Mo layer during high temperature selenization. • The formation of MoSe{sub 2} layer was precisely controlled. • The diffusion barrier performance of MoN{sub x} against Se was evaluated using TEM analysis. - Abstract: This study investigated the interfacial reactions and electrical properties of a Mo single layer and Mo/MoN{sub x}/Mo multilayer during high temperature selenization annealing. The Mo single layer was converted easily to MoSe{sub 2}, which was 7 times thicker than the Mo layer consumed ∼900 nm, by selenization at 460 °C for 10 min and the sheet resistance increased 8 fold compared to that of the as-deposited Mo film. On the other hand, in the Mo/MoN{sub x}/Mo structure, transmission electron microscopy (TEM) showed that the MoSe{sub 2} transformation was localized only in the top Mo layer and the bottom Mo layer was completely unaffected, even after selenization at 560 °C. The sheet resistance of the multilayer was relatively unchanged by selenization. This suggests that the MoN{sub x} layer performed well as a diffusion barrier against Se and the thickness of MoSe{sub 2} can be controlled precisely by adjusting the top Mo layer thickness. Furthermore, TEM and energy dispersive spectroscopy analysis showed that the selenized multilayer consisted of MoSe{sub 2}/Mo/MoN{sub x}/Mo, in which the top Mo layer of 60 nm was not fully converted to MoSe{sub 2} and 20 nm was left unreacted. The residual Mo interlayer located at the interface of MoSe{sub 2} and MoN{sub x} is believed to be beneficial for the ohmic contact of the selenized multilayer.

Structure and spectroscopy of uranyl salicylaldiminate complexes

Energy Technology Data Exchange (ETDEWEB)

Tamasi, A.L.; Barnes, C.L.; Walensky, J.R. [Missouri Univ., Columbia, MO (United States). Dept. of Chemistry

2013-07-01

The synthesis of uranyl complexes coordinated to tridentate, monoanionic salicylaldiminate (Schiff base) ligands was achieved by the reaction of UO{sub 2}Cl{sub 2}(THF){sub 3}, 1, with one equivalent of the corresponding sodium salicylaldiminate salts affording [(C{sub 9}H{sub 6}N)N=C(H)C{sub 6}H{sub 2}'Bu{sub 2}O]UO{sub 2}Cl(THF), 2, [(NC{sub 5}H{sub 4})N=C(H)C{sub 6}H{sub 2}'Bu{sub 2}O]UO{sub 2}Cl(THF), 3, and [(C{sub 6}H{sub 4}SCH{sub 3})N=C(H)C{sub 6}H{sub 2}'Bu{sub 2}O]UO{sub 2}Cl(THF), 4. These are uncommon examples of uranyl complexes with a monoanionic ancillary ligand to stabilize the coordination sphere and one chloride ligand. Compounds 2-4 have been characterized by {sup 1}H and {sup 13}C NMR spectroscopy as well as IR and UVVis spectroscopy and their structures determined by X-ray crystallography. (orig.)

Uranyl oxo activation and functionalization by metal cation coordination

Energy Technology Data Exchange (ETDEWEB)

Arnold Polly, L; Pecharman, A F; Hollis, E; Parsons, S; Love, J B [Univ Edinburgh, EaStCHEM Sch Chem, Edinburgh EH9 3JJ, Midlothian (United Kingdom); Yahia, A; Maron, L [Univ Toulouse 3, LPCNO, UMR 5215, INSA, CNRS, F-31077 Toulouse 4 (France); Yahia, A; Maron, L [Univ Montpellier 2, ENSCM, CNRS, ICSM, UMR 5257, CEA, Ctr Marcoule, F-30207 Bagnols Sur Ceze (France)

2010-07-01

The oxo groups in the uranyl ion [UO{sub 2}]{sup 2+} - one of many oxo cations formed by metals from across the periodic table - are particularly inert, which explains the dominance of this ion in the laboratory and its persistence as an environmental contaminant. In contrast, transition metal oxo (M=O) compounds can be highly reactive and carry out difficult reactions such as the oxygenation of hydrocarbons. Here we show how the sequential addition of a lithium metal base to the uranyl ion constrained in a 'Pacman' environment results in lithium coordination to the U=O bonds and single-electron reduction. This reaction depends on the nature and stoichiometry of the lithium reagent and suggests that competing reduction and C-H bond activation reactions are occurring. (authors)

Formation of CuInSe{sub 2} films from metal sulfide and selenide precursor nanocrystals by gas-phase selenization, an in-situ XRD study

Energy Technology Data Exchange (ETDEWEB)

Capon, B., E-mail: boris.capon@ugent.be [Department of Solid State Sciences, Ghent University, Krijgslaan 281-S1, B-9000 Ghent (Belgium); Dierick, R. [Physics and Chemistry of Nanostructures, Ghent University, Krijgslaan 281-S3, B-9000 Ghent (Belgium); Hens, Z. [Physics and Chemistry of Nanostructures, Ghent University, Krijgslaan 281-S3, B-9000 Ghent (Belgium); Center for Nano and Biophotonics, Ghent University, Ghent (Belgium); Detavernier, C. [Department of Solid State Sciences, Ghent University, Krijgslaan 281-S1, B-9000 Ghent (Belgium)

2016-08-01

In this work phase pure CuInSe{sub 2} thin flms were obtained by selenization of ternary CuInSe{sub 2} and CuInS{sub 2} nanocrystals and mixtures of binary nanocrystals such as CuS, In{sub 2}S{sub 3}, Cu{sub 2}Se and In{sub 2}Se{sub 3}. The temperature of the selenium source was kept at 400 °C during selenization. Monitoring the process using in-situ x-ray diffraction, the effect of selenization on the phase formation and grain growth in the precursor film was investigated. Whereas CuInSe{sub 2} and CuInS{sub 2} nanocrystals exhibit little grain growth, we found that mixtures of binary nanocrystals can show significant sintering depending on the reaction conditions. For the mixture of CuS and In{sub 2}S{sub 3} nanocrystals, the crystallinity and the morphology of the obtained fims strongly depends on the Cu/In ratio, with a Cu excess strongly promoting grain growth. With mixtures of Cu{sub 2}Se and In{sub 2}Se{sub 3} nanocrystals the selenium partial pressure plays a crucial role. Selenium evaporation from the mixed compounds results in CuInSe{sub 2} films composed of relatively small crystallites. Higher selenium partial pressures however resulted in improved sintering. Incomplete propagation of the selenization reaction through the layer was observed though, only leading to a well sintered CuInSe{sub 2} top layer above a fine grained bottom layer. - Highlights: • Different types of colloidal nanocrystals were used as precursors to obtain CuInSe{sub 2} films by gas-phase selenization. • In-situ XRD was used to study the effect of selenization on the phase formation and grain growth in the precursor films. • For a mixture of binary metal sulfides the crystallinity and the morphology strongly depend on the Cu/In ratio. • Higher selenium partial pressures result in improved sintering for a mixture of binary metal selenides.

Complete removal of uranyl nitrate from tissue matrix using supercritical fluid extraction

International Nuclear Information System (INIS)

Kumar, R.; Sivaraman, N.; Senthil Vadivu, E.; Srinivasan, T.G.; Vasudeva Rao, P.R.

2003-01-01

The removal of uranyl nitrate from tissue matrix has been studied with supercritical carbon dioxide modified with methanol alone as well as complexing reagents dissolved in methanol. A systematic study of various complexing agents led to the development of an extraction procedure for the quantitative recovery of uranium from tissue matrix with supercritical carbon dioxide modified with methanol containing small quantities of acetylacetone. The drying time and temperature employed in loading of uranyl nitrate onto tissue paper were found to influence the extraction efficiency significantly

Cyclic phosphopeptides to rationalize the role of phosphoamino acids in uranyl binding to biological targets

Energy Technology Data Exchange (ETDEWEB)

Starck, Matthieu; Laporte, Fanny A.; Oros, Stephane; Sisommay, Nathalie; Gathu, Vicky; Lebrun, Colette; Delangle, Pascale [INAC/SyMMES, UMR5819, Universite Grenoble Alpes, CEA, CNRS, Grenoble (France); Solari, Pier Lorenzo [Synchrotron SOLEIL, L' orme des Merisiers, Saint-Aubin, Gif-sur-Yvette (France); Creff, Gaelle; Den Auwer, Christophe [Institut de Chimie de Nice, UMR7272, Universite Cote d' Azur, Nice (France); Roques, Jerome [Institut de Physique Nucleaire d' Orsay, CNRS-IN2P3, Univ. Paris-Sud, Universite Paris-Saclay (France)

2017-04-19

The specific molecular interactions responsible for uranium toxicity are not yet understood. The uranyl binding sites in high-affinity target proteins have not been identified yet and the involvement of phosphoamino acids is still an important question. Short cyclic peptide sequences, with three glutamic acids and one phosphoamino acid, are used as simple models to mimic metal binding sites in phosphoproteins and to help understand the mechanisms involved in uranium toxicity. A combination of peptide design and synthesis, analytical chemistry, extended X-ray absorption fine structure (EXAFS) spectroscopy, and DFT calculations demonstrates the involvement of the phosphate group in the uranyl coordination sphere together with the three carboxylates of the glutamate moieties. The affinity constants measured with a reliable analytical competitive approach at physiological pH are significantly enhanced owing to the presence of the phosphorous moiety. These findings corroborate the importance of phosphoamino acids in uranyl binding in proteins and the relevance of considering phosphoproteins as potential uranyl targets in vivo. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Reaction of uranyl nitrate with carboxylic di-acids under hydrothermal conditions. Crystal structure of complexes with L(+)-tartaric and oxalic acids

International Nuclear Information System (INIS)

Thuery, P.

2007-01-01

L(+)-tartaric acid reacts with uranyl nitrate in the presence of KOH, under mild hydrothermal conditions, to give the complex [UO 2 (C 4 H 4 O 6 )(H 2 O)] (1), the first uranyl tartrate to be crystallographically characterized. Each tartrate ligand bridges three uranyl ions, one of them in chelating fashion through proximal carboxylate and hydroxyl groups. The resulting assemblage is two-dimensional, with the uranyl pentagonal bipyramidal coordination polyhedra separated from one another. Prolonged heating of an uranyl tartrate solution resulted in oxidative cleavage of the acid and formation of the oxalate complex [(UO 2 ) 2 (C 2 O 4 ) 2 (OH)Na(H 2 O) 2 ] (2). The bis-bidentate oxalate and bridging hydroxide groups ensure the formation of sheets with corner-sharing uranyl pentagonal bipyramidal coordination polyhedra, in which six-membered metallacycles encompass the sodium ions. These sheets are assembled into a three-dimensional framework through further oxo-bonding of the sodium ions. (authors)

Synthesis, X-ray crystallography, thermal studies, spectroscopic and electrochemistry investigations of uranyl Schiff base complexes.

Science.gov (United States)

Asadi, Zahra; Shorkaei, Mohammad Ranjkesh

2013-03-15

Some tetradentate salen type Schiff bases and their uranyl complexes were synthesized and characterized by UV-Vis, NMR, IR, TG, C.H.N. and X-ray crystallographic studies. From these investigations it is confirmed that a solvent molecule occupied the fifth position of the equatorial plane of the distorted pentagonal bipyramidal structure. Also, the kinetics of complex decomposition by using thermo gravimetric methods (TG) was studied. The thermal decomposition reactions are first order for the studied complexes. To examine the properties of uranyl complexes according to the substitutional groups, we have carried out the electrochemical studies. The electrochemical reactions of uranyl Schiff base complexes in acetonitrile were reversible. Copyright © 2012 Elsevier B.V. All rights reserved.

Controlled deprotection and reorganization of uranyl oxo groups in a binuclear macrocyclic environment

International Nuclear Information System (INIS)

Jones, Guy M.; Arnold, Polly L.; Love, Jason B.

2012-01-01

The silylated uranium(V) dioxo complex [(Me_3SiOUO)_2(L)_2] is inert to oxidation, but after two-electron reduction to [(Me_3SiOUO)_2(L)]"2"-, it can be desilylated to form [OU(μ-O)_2UO(L)_2]"2"- with reinstated uranyl character. Removal of the silyl group uncovers new redox and oxo rearrangement chemistry for uranium, thus reforming the uranyl motif and involving the U"V"I"/"V couple in dioxygen reduction. [de

SEPARATION OF BARIUM VALUES FROM URANYL NITRATE SOLUTIONS

Science.gov (United States)

Tompkins, E.R.

1959-02-24

The separation of radioactive barium values from a uranyl nitrate solution of neutron-irradiated uranium is described. The 10 to 20% uranyl nitrate solution is passed through a flrst column of a cation exchange resin under conditions favoring the adsorption of barium and certain other cations. The loaded resin is first washed with dilute sulfuric acid to remove a portion of the other cations, and then wash with a citric acid solution at pH of 5 to 7 to recover the barium along with a lesser amount of the other cations. The PH of the resulting eluate is adjusted to about 2.3 to 3.5 and diluted prior to passing through a smaller second column of exchange resin. The loaded resin is first washed with a citric acid solution at a pH of 3 to elute undesired cations and then with citric acid solution at a pH of 6 to eluts the barium, which is substantially free of undesired cations.

Uranyl nitrate-exposed rat alveolar macrophages cell death: Influence of superoxide anion and TNF α mediators

International Nuclear Information System (INIS)

Orona, N.S.; Tasat, D.R.

2012-01-01

Uranium compounds are widely used in the nuclear fuel cycle, military and many other diverse industrial processes. Health risks associated with uranium exposure include nephrotoxicity, cancer, respiratory, and immune disorders. Macrophages present in body tissues are the main cell type involved in the internalization of uranium particles. To better understand the pathological effects associated with depleted uranium (DU) inhalation, we examined the metabolic activity, phagocytosis, genotoxicity and inflammation on DU-exposed rat alveolar macrophages (12.5–200 μM). Stability and dissolution of DU could differ depending on the dissolvent and in turn alter its biological action. We dissolved DU in sodium bicarbonate (NaHCO 3 100 mM) and in what we consider a more physiological vehicle resembling human internal media: sodium chloride (NaCl 0.9%). We demonstrate that uranyl nitrate in NaCl solubilizes, enters the cell, and elicits its cytotoxic effect similarly to when it is diluted in NaHCO 3 . We show that irrespective of the dissolvent employed, uranyl nitrate impairs cell metabolism, and at low doses induces both phagocytosis and generation of superoxide anion (O 2 − ). At high doses it provokes the secretion of TNFα and through all the range of doses tested, apoptosis. We herein suggest that at DU low doses O 2 − may act as the principal mediator of DNA damage while at higher doses the signaling pathway mediated by O 2 − may be blocked, prevailing damage to DNA by the TNFα route. The study of macrophage functions after uranyl nitrate treatment could provide insights into the pathophysiology of uranium‐related diseases. -- Highlights: ► Uranyl nitrate effect on cultured macrophages is linked to the doses and independent of its solubility. ► At low doses uranyl nitrate induces generation of superoxide anion. ► At high doses uranyl nitrate provokes secretion of TNFα. ► Uranyl nitrate induces apoptosis through all the range of doses tested.

Uranyl nitrate-exposed rat alveolar macrophages cell death: Influence of superoxide anion and TNF α mediators

Energy Technology Data Exchange (ETDEWEB)

Orona, N.S. [School of Science and Technology, National University of General Martín, Avda Gral Paz 5445 (1650) San Martín, Buenos Aires (Argentina); Tasat, D.R., E-mail: deborah.tasat@unsam.edu.ar [School of Science and Technology, National University of General Martín, Avda Gral Paz 5445 (1650) San Martín, Buenos Aires (Argentina); School of Dentistry, University of Buenos Aires, M. T. de Alvear 2142 (1122), Buenos Aires (Argentina)

2012-06-15

Uranium compounds are widely used in the nuclear fuel cycle, military and many other diverse industrial processes. Health risks associated with uranium exposure include nephrotoxicity, cancer, respiratory, and immune disorders. Macrophages present in body tissues are the main cell type involved in the internalization of uranium particles. To better understand the pathological effects associated with depleted uranium (DU) inhalation, we examined the metabolic activity, phagocytosis, genotoxicity and inflammation on DU-exposed rat alveolar macrophages (12.5–200 μM). Stability and dissolution of DU could differ depending on the dissolvent and in turn alter its biological action. We dissolved DU in sodium bicarbonate (NaHCO{sub 3} 100 mM) and in what we consider a more physiological vehicle resembling human internal media: sodium chloride (NaCl 0.9%). We demonstrate that uranyl nitrate in NaCl solubilizes, enters the cell, and elicits its cytotoxic effect similarly to when it is diluted in NaHCO{sub 3}. We show that irrespective of the dissolvent employed, uranyl nitrate impairs cell metabolism, and at low doses induces both phagocytosis and generation of superoxide anion (O{sub 2}{sup −}). At high doses it provokes the secretion of TNFα and through all the range of doses tested, apoptosis. We herein suggest that at DU low doses O{sub 2}{sup −} may act as the principal mediator of DNA damage while at higher doses the signaling pathway mediated by O{sub 2}{sup −} may be blocked, prevailing damage to DNA by the TNFα route. The study of macrophage functions after uranyl nitrate treatment could provide insights into the pathophysiology of uranium‐related diseases. -- Highlights: ► Uranyl nitrate effect on cultured macrophages is linked to the doses and independent of its solubility. ► At low doses uranyl nitrate induces generation of superoxide anion. ► At high doses uranyl nitrate provokes secretion of TNFα. ► Uranyl nitrate induces apoptosis through

Synthesis and characterization of functional copolymer/organo-silicate nanoarchitectures through interlamellar complex-radical (coterpolymerization

Directory of Open Access Journals (Sweden)

2008-09-01

Full Text Available The functional copolymers, having a combination of rigid/flexible linkages and an ability of complex-formation with interlayered surface of organo-silicate, and their nanocomposites have been synthesized by interlamellar complex-radical (coterpolymerization of intercalated monomer complexes of maleic anhydride (MA and itaconic acid (IA with dimethyl dodecylamine surface modified montmorillonite (organo-MMT (MA…DMDA-MMT and IA…DMDA-MMT n-butyl methacrylate (BMA and/or BMA/styrene monomer mixtures. The results of nanocomposite structure–composition– property relationship studies indicate that interlamellar complex-formation between anhydride/acid units and surface alkyl amine and rigid/flexible linkage balance in polymer chains are important factors providing the effective intercalation/ exfoliation of the polymer chains into the silicate galleries, the formation of nanostructural hybrids with higher thermal stability, dynamic mechanical behaviour and well dispersed morphology.

Effects of sawdust and organo mineral fertilizer and their residual effect on the yield of maize on degrades soil

International Nuclear Information System (INIS)

Dania, S.O.; Fagbola, O.; Isitekhale, H.H.E.

2012-01-01

Conventional mineral fertilizer alone cannot sustain arable crop production in soil which top layer has been eroded hence it is necessary to employ the application of organic base fertilizer. A greenhouse experiment was conducted to investigate the effects of sawdust, organo mineral fertilizer and their residual effects on the growth and yield of maize. Organo mineral fertilizer is the combination of organic manure and mineral fertilizer. Simulated degraded soil was used and the experimental design was a 2 x 2 x 3 factorial in a completely randomized design with three replicates. The factors investigated were: two levels of organo mineral fertilizer (with and without), two levels of soil amendment (with and without sawdust) and three levels of application methods. The methods of organo mineral fertilizer used were ring, subsurface and mixed methods. The amendment of soil to sawdust was ratio 1:1 by volume. The growth and yield of maize was significantly (p = 0.05) higher in non-amended soil with OMF under different application methods compared to soil amended with sawdust with or without OMF application. Ring method of application of OMF in non-amended soil significantly increased the growth and yield of maize compared to other methods of OMF application. The residual effect of OMF and sawdust on the growth and yield of maize was significantly higher in non-amended soil with OMF under different application methods compared to soil amended with sawdust. Addition of sawdust to soil does not improve the growth and yield of maize with or without OMF and under different application methods. Organo mineral fertilizer using ring and subsurface application methods has a beneficial effect in improving the growth and yield of maize in degraded soil where the top layer has been eroded. (author)

Effects of sawdust and organo mineral fertilizer and their residual effect on the yield of maize on degraded soil

International Nuclear Information System (INIS)

Dania, S.O.; Fagbola, O.

2012-01-01

Conventional mineral fertilizer alone cannot sustain arable crop production in soil which top layer has been eroded hence it is necessary to employ the application of organic base fertilizer. A greenhouse experiment was conducted to investigate the effects of sawdust, organo mineral fertilizer and their residual effects on the growth and yield of maize. Organo mineral fertilizer is the combination of organic manure and mineral fertilizer. Simulated degraded soil was used and the experimental design was a 2 x 2 x 3 factorial in a completely randomized design with three replicates. The factors investigated were: two levels of organo mineral fertilizer (with and without), two levels of soil amendment (with and without sawdust) and three levels of application methods. The methods of organo mineral fertilizer used were ring, subsurface and mixed methods. The amendment of soil to sawdust was ratio 1: 1 by volume. The growth and yield of maize was significantly (p = 0.05) higher in non-amended soil with OMF under different application methods compared to soil amended with sawdust with or without OMF application. Ring method of application of OMF in non-amended soil significantly increased the growth and yield of maize compared to other methods of OMF application. The residual effect of OMF and sawdust on the growth and yield of maize was significantly higher in non-amended soil with OMF under different application methods compared to soil amended with sawdust. Addition of sawdust to soil does not improve the growth and yield of maize with or without OMF and under different application methods. Organo mineral fertilizer using ring and subsurface application methods has a beneficial effect in improving the growth and yield of maize in degraded soil where the top layer has been eroded. (author)

Effects of nitrate, fulvate, phosphate, phthalate, salicylate and catechol on the sorption of uranyl onto SiO2. A comparative study

International Nuclear Information System (INIS)

Zhang Hongxia; Wen Chuanxi; Tao Zuyi; Wu Wangsuo

2011-01-01

We have performed a large number of batch sorption experiments of uranyl onto SiO 2 and examined the effects of nitrate or ionic strength, phosphate, fulvic acid(FA), phthalic acid (PH), salicylic acid (SA), and catechol (CA) on the uranyl sorption onto SiO 2 . Three sorption edges and three sorption isotherms at ionic strengths 0.05, 0.1, and 0.5 mol/L KNO 3 were used to investigate the effect of ionic strength or nitrate on the sorption and the Langmuir, Freundlich, and Dubinin-Radushkevich models are used to simulate the sorption isotherms, respectively. Five sorption edges in the presence of phosphate, FA, PH, SA, and CA were compared with that in the absence of complexing ligand. The results suggest that the effect of complexation of uranyl with nitrate on the uranyl sorption can be negligible and the sorption can be described Freundlich and D-R model very well. The positive effect of phosphate on the uranyl sorption was found, though the extent of effect was decreased with increasing pH. The positive effect and the negative effect of FA on the uranyl sorption were found at low pH and high pH ranges, respectively. The sorption edge of uranyl sorption remained unaffected in the presence of PH in the pH 2-10. In the presence of SA, the no effect and the negative effect on the uranyl sorption were, respectively, found at low pH and high pH ranges. The negative effect of CA on the uranyl sorption was found in the pH 2-10. (author)

Bioavailability of selenium from fish, yeast and selenate: A comparative study in humans using stable isotopes

NARCIS (Netherlands)

Fox, T.E.; Heuvel, E.G.H.M. van den; Atherton, C.A.; Dainty, J.R.; Lewis, D.J.; Langford, N.J.; Crews, H.M.; Luten, J.B.; Lorentzen, M.; Sieling, F.W.; Aken-Schneyder, P. van; Hoek, M.; Kotterman, M.J.J.; Dael, P. van; Firweather-Tail, S.J.

2004-01-01

Objective: To measure the bioavailability of selenium from cooked and raw fish in humans by estimating and comparing apparent absorption and retention of selenium in biosynthetically labelled fish with labelled selenate and biosynthetically labelled selenium in brewers yeast. Design: The

Bioavailibility of selenium from fish, yeast and selenate: a comparative study in humans using stable isotopes

NARCIS (Netherlands)

Fox, T.E.; Heuvel, van den E.G.H.M.; Atherton, C.A.; Luten, J.B.; Hoek-van Nieuwenhuizen, van M.; Kotterman, M.J.J.

2004-01-01

Objective: To measure the bioavailability of selenium from cooked and raw fish in humans by estimating and comparing apparent absorption and retention of selenium in biosynthetically labelled fish with labelled selenate and biosynthetically labelled selenium in brewers yeast. Design: The

The Effect of E-Selen Antioxidant on the Fatty Acids Content of the Homogenate of Unirradiated and Irradiated Pupae of Ceratitis Capitata

International Nuclear Information System (INIS)

Zaghloul, Y.S.; Abbassy, S.A.; Elakhdar, E.A.H.; Elakhdar, E.A.H.

2011-01-01

As antioxidant E-selen was added to the larval artificial diets of the Mediterranean fruit fly, Ceratitis capitata. The produced full grown pupae were exposed to gamma rays at dose rate of 90 Gy. The fatty acid contents of the normal and irradiated insects were analyzed to test to what extent, the uptake of the antioxidant will ameliorate the physiological damage induced to the medfly pupae, as a result of their exposure to irradiation. The results obtained by using Gas-liquid chromatography of fatty acid methyl esters, showed the palmitic and oleic acids to be the most predominant fatty acids in all pupal homogenates in both normal and irradiated pupae, either by the uptake of doses of the E-selen or without. The uptake of E-Selen with a dose of 0.3 mg led to a complete absence of the lauric and myristic acids in the homogenates of the unirradiated pupae of the medfly. This absence of lauric and myristic acids was accompanied by a decrease in the concentrations of the palmitic and linoleic acids reaching 25.17% and 32.98%, respectively as compared to pupae without the uptake of antioxidant. The concentrations of both the stearic and oleic acids showed an obvious increment reaching 199.22% and 58.94%, respectively, relative to those reared on the defined media and no added E.Selen. Exposure of the pupae to a dose of 90 Gy, resulted in an increment in the concentrations of the saturated lauric and myristic acid reaching 96.77% and 34.07%, respectively, relative to the untreated ones. While, at the same dose level, there were decrements in the concentrations of the palmitic, stearic, oleic and linoleic acids with percentages reaching 6.4, 9.22, 3.65 and 1.15%, respectively as compared to unirradiated controls. Irradiation of the pupae with sterilizing dose (90 Gy) after up taking the E-Selen in their larval diets, led to the increase of the concentrations of lauric, oleic and linoleic acids by ratios of 16.82, 8.84 and 29.26%, respectively as compared to their

Synthesis of pyrimidine carboxamide derivatives catalyzed by uranyl

African Journals Online (AJOL)

2014-09-02

(Received September 2, 2014; revised January 1, 2016). ABSTRACT. An efficient and simple method was developed for the synthesis pyrimidine-5-carboxamides using. UO2(NO3)2.6H2O catalyst under conventional and microwave irradiation. The synthesis of dihydropyrimidine using uranyl nitrate had shown many ...

Removal of uranyl ions by p-hexasulfonated calyx[6]arene acid

Energy Technology Data Exchange (ETDEWEB)

Popescu, Ioana-Carmen [R and D National Institute for Metals and Radioactive Resources–ICPMRR, B-dul Carol I No.70, Sector 2, Bucharest 020917 (Romania); Petru, Filip [“C.D. Nenitescu” Institute of Organic Chemistry, Splaiul Independentei 202B, Sector 6, Bucharest 71141 (Romania); Humelnicu, Ionel [“Al.I. Cuza” University of Iasi, The Faculty of Chemistry, Bd. Carol-I No. 11, Iasi 700506 (Romania); Mateescu, Marina [National R and D Institute for Chemistry and Petrochemistry, Splaiul Independenţei No. 202, Bucharest 060021 (Romania); Militaru, Ecaterina [R and D National Institute for Metals and Radioactive Resources–ICPMRR, B-dul Carol I No.70, Sector 2, Bucharest 020917 (Romania); Humelnicu, Doina, E-mail: doinah@uaic.ro [“Al.I. Cuza” University of Iasi, The Faculty of Chemistry, Bd. Carol-I No. 11, Iasi 700506 (Romania)

2014-10-15

Radioactive pollution is a significant threat for the people’s health. Therefore highly effective radioactive decontamination methods are required. Ion exchange, biotechnologies and phytoremediation in constructed wetlands have been used as radioactive decontamination technologies for uranium contaminated soil and water remediation. Recently, beside those classical methods the calix[n]arenic derivatives’ utilization as radioactive decontaminators has jogged attention. The present work aims to present the preliminary research results of uranyl ion sorption studies on the p-hexasulfonated calyx[6]arenic acid. The effect of temperature, contact time, sorbent amount and uranyl concentration variation on sorption efficiency was investigated. Isotherm models revealed that the sorption process fit better Langmuir isotherm.

Studies on conductance of uranyl soaps

International Nuclear Information System (INIS)

Mehrotra, K.N.; Sharma, M.; Gahlaut, A.S.

1987-01-01

Specific conductance of uranyl soaps in dimethylformamide indicates two critical micelle concentrations CMC(I) and CMC(II). The value of CMC(II) decreases with the increase in chain length of the soap, whereas CMC(I) does not vary at all. The results show that the soaps behave as simple electrolyte. The major conductance at infinite dilution (μsub(o)) and dissociation constant (K) of these soaps have been evaluated. (author). 12 refs

Density Functional Studies on the Complexation and Spectroscopy of Uranyl Ligated with Acetonitrile and Acetone Derivatives

International Nuclear Information System (INIS)

Schoendorff, George E.; Windus, Theresa L.; De Jong, Wibe A.

2009-01-01

The coordination of nitrile (acetonitrile, propionitrile, and benzonitrile) and carbonyl (formaldehyde, ethanal, and acetone) ligands to the uranyl dication (UO22+) has been examined using density functional theory (DFT) utilizing relativistic effective core potentials (RECPs). Complexes containing up to six ligands have been modeled for all ligands except formaldehyde, for which no minimum could be found. A comparison of relative binding energies indicates that five coordinate complexes are predominant while a six coordinate complex involving propionitrile ligands might be possible. Additionally, the relative binding energy and the weakening of the uranyl bond is related to the size of the ligand and, in general, nitriles bind more strongly to uranyl than carbonyls.

Uptake of selenate on hydrated and degraded cement: batch and dynamic experiments

International Nuclear Information System (INIS)

Rojo, I.; Rovira, I.; Marti, V.; Pablo, J. de; Duro, L.; Gaona, X.; Colas, E.; Grive, M.

2009-01-01

The evaluation of selenate sorption and retardation in batch and dynamic experiments on hydrated and degraded cement has been studied. Desorption studies have also been carried in order to assess the reversibility of the sorption process. Sorption data onto degraded cement have been treated assuming the formation of surface complexes, whereas sorption kinetics has been fitted by using a pseudo-first order kinetic equation. Dynamic flow experiments have also been modelled. (authors)

Enhancement of uranyl fluorescence using trimesic acid: Ligand sensitization and co-fluorescence

Energy Technology Data Exchange (ETDEWEB)

Maji, S. [Chemistry Group, Materials Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India); Viswanathan, K.S., E-mail: vish@igcar.gov.in [Chemistry Group, Materials Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India)

2011-09-15

Trimesic acid (TMA) was shown to sensitize and enhance uranyl fluorescence in aqueous medium, with the enhancement being a maximum at pH 5.0. Fluorescence spectra and lifetime data together suggest that TMA complexes with uranyl (UO{sub 2}{sup 2+}). The fluorescence of UO{sub 2}{sup 2+} in its acid complex is further enhanced by more than two orders of magnitude following the addition of Y{sup 3+}; a process referred to as co-fluorescence, leading to the possibility of detecting uranium at sub ng/mL level. The present study demonstrates, for the first time, fluorescence enhancement of the uranyl species due to co-fluorescence. - Highlights: > Trimesic acid was shown to sensitize and enhance the fluorescence of uranium in aqueous medium. > This ligand also exhibited co-fluorescence of uranium with Y{sup 3+}. > To the best of our knowledge this is the first report of co-fluorescence in uranium. > The enhancement of uranium fluorescence, resulted in detection limits in the ng/mL regime.

Preparation of Cu{sub 2}ZnSnSe{sub 4} solar cells by low-temperature co-evaporation and following selenization

Energy Technology Data Exchange (ETDEWEB)

Gao, Chao, E-mail: chao.gao@kit.edu; Hetterich, Michael [Institute of Applied Physics, Karlsruhe Institute of Technology (KIT), 76131 Karlsruhe (Germany); Schnabel, Thomas; Abzieher, Tobias; Ahlswede, Erik [Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg (ZSW), 70565 Stuttgart (Germany); Powalla, Michael [Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg (ZSW), 70565 Stuttgart (Germany); Light Technology Institute (LTI), Karlsruhe Institute of Technology (KIT), 76131 Karlsruhe (Germany)

2016-01-04

Cu{sub 2}ZnSnSe{sub 4} (CZTSe) thin films are prepared by a two-step method which involves co-evaporation of Cu, Zn, Sn, and Se on molybdenum-coated soda-lime glass at low substrate temperature and a following selenization. Solar cells with efficiencies of up to 6.5% can be achieved. The influence of the selenium deposition rates during co-evaporation and the nitrogen pressure during selenization on the properties of the CZTSe films are investigated. It is found that these two parameters can significantly affect the morphology and crystallinity of the CZTSe films. The possible reasons for the experimental results are discussed.

Electrospray ionization of uranyl-citrate complexes

Science.gov (United States)

Somogyi, Árpád; Pasilis, Sofie P.; Pemberton, Jeanne E.

2007-09-01

Results presented here demonstrate the usefulness of electrospray ionization and gas-phase ion-molecule reactions to predict structural and electronic differences in complex inorganic ions. Electrospray ionization of uranyl citrate solutions generates positively and negatively charged ions that participate in further ion-molecule reactions in 3D ion trap and FT-ICR mass analyzers. Most ions observed are derived from the major solution uranyl-citrate complexes and involve species of {(UO2)2Cit2}2-, (UO2)3Cit2, and {(UO2)3Cit3}3-, where Cit indicates the citrate trianion, C6H5O73-. In a 3D ion trap operated at relatively high pressure, complex adducts containing solvent molecules, alkali and ammonium cations, and nitrate or chloride anions are dominant, and proton/alkali cation (Na+, K+) exchange is observed for up to six exchangeable protons in an excess of alkali cations. Adduct formation in a FT-ICR cell that is operated at lower pressures is less dominant, and direct detection of positive and negative ions of the major solution complexes is possible. Multiply charged ions are also detected, suggesting the presence of uranium in different oxidation states. Changes in uranium oxidation state are detected by He-CID and SORI-CID fragmentation, and certain fragments undergo association reactions in trapping analyzers, forming "exotic" species such as [(UO2)4O3]-, [(UO2)4O4]-, and [(UO2)4O5]-. Ion-molecule reactions with D2O in the FT-ICR cell indicate substantial differences in H/D exchange rate and D2O accommodation for different ion structures and charge states. Most notably, the positively charged ions [H2(UO2)2Cit2(H)]+ and [(UO2)2(Cit)]+ accommodate two and three D2O molecules, respectively, which reflects well the structural differences, i.e., tighter uranyl-citrate coordination in the former ion than in the latter. The corresponding negatively charged ions accommodate zero or two D2O molecules, which can be rationalized using suggested solution phase structures

Uranyl complexes as scaffolding or spacers for cucurbit[6]uril molecules in homo- and heterometallic species, including a uranyl-lanthanide complex

Energy Technology Data Exchange (ETDEWEB)

Thuery, Pierre [NIMBE, CEA, CNRS, Universite Paris-Saclay, CEA Saclay, Gif-sur-Yvette (France)

2017-06-16

The reaction of uranyl nitrate with cucurbit[6]uril (CB6) and carboxylic or sulfonic ligands under hydrothermal conditions and in the presence of additional metal cations (K{sup I} or Ce{sup III}) or cosolvents provided four complexes, which were crystallographically characterized. The compound [(UO{sub 2}){sub 2}K{sub 2}(CB6)(adc){sub 2}(NO{sub 3}){sub 2}(H{sub 2}O){sub 2}].5H{sub 2}O (1), where H{sub 2}adc is 1,3-adamantanedicarboxylic acid, crystallizes in the form of a central K{sub 2}(CB6){sup 2+} column surrounded by two one-dimensional (1D) polymeric UO{sub 2}(adc)(NO{sub 3}){sup -} chains attached to the column by nitrate bridges, with a perfect match of the repeat lengths in the two subunits. The longer 1,3-adamantanediacetic acid (H{sub 2}adac) gives the complex [(UO{sub 2}){sub 2}(adac){sub 2}(HCOOH){sub 2}].CB6.6H{sub 2}O (2), in which the 1D uranyl-containing polymer and columns of CB6 molecules form a layered arrangement held by weak CH..O hydrogen bonds. The complex formed with the dipotassium salt of methanedisulfonic acid (K{sub 2}mds), [(UO{sub 2}){sub 2}K{sub 2}(CB6)(mds){sub 2}(OH){sub 2}(H{sub 2}O){sub 8}].4H{sub 2}O (3), is a 1D polymer, in which K{sub 2}(CB6){sup 2+} units are connected to one another by doubly hydroxide-bridged uranyl dimers in which the disulfonates are terminal, chelating ligands; connection between the two subunits is solely through potassium oxo-bonding to uranyl. The complex [(UO{sub 2}){sub 2}Ce{sub 2}(CB6)(C{sub 2}O{sub 4}){sub 3}(NO{sub 3}){sub 4}(H{sub 2}O){sub 6}].2H{sub 2}O (4) is a 1D polymer containing bridging oxalate ligands formed in situ, in which CB6 is coordinated to the lanthanide cations only; one nitrate ligand and one water ligand, hydrogen-bonded to each other, are included in the CB6 cavity, with the possible occurrence of interactions between nitrate oxygen atoms and ureido carbon atoms. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Water-Reflected 233U Uranyl Nitrate Solutions in Simple Geometry

International Nuclear Information System (INIS)

Elam, K.R.

2001-01-01

A number of critical experiments involving 233 U were performed in the Oak Ridge National Laboratory Building 9213 Critical Experiments Facility during the years 1952 and 1953. These experiments, reported in Reference 1, were directed toward determining bounding values for the minimum critical mass, minimum critical volume, and maximum safe pipe size of water-moderated solutions of 233 U. Additional information on the critical experiments was found in the experimental logbooks. Two experiments utilizing uranyl nitrate (UO 2 (NO 3 ) 2 ) solutions in simple geometry are evaluated in this report. Experiment 37 is in a 10.4-inch diameter sphere, and Experiment 39 is in a 10-inch diameter cylinder. The 233 U concentration ranges from 49 to 62 g 233 U/l. Both experiments were reflected by at least 6 inches of water in all directions. Paraffin-reflected uranyl nitrate experiments, also reported in Reference 1, are evaluated elsewhere. Experiments with smaller paraffin reflected 5-, 6-, and 7.5-inch diameter cylinders are evaluated in U233-SOL-THERM-004. Experiments with paraffin reflected 8-, 8.5-, 9-, 10-, and 12-inch diameter cylinders are evaluated in U233-SOL-THERM-002. Later experiments with highly-enriched 235 U uranyl fluoride solution in the same 10.4-inch diameter sphere are reported in HEU-SOL-THERM-010. Both experiments were judged acceptable for use as criticality-safety benchmark experiments

Identifying the Impact of E-Selen on the Sterile Medfly Ceratitis capitata at the Genomic Level Using DNA Profile

International Nuclear Information System (INIS)

Zaghloul, Y.S.

2014-01-01

The antioxidant E-Selen is an exogenous antioxidant containing both selenium and vitamin E. It was added to the larval artificial diets of the Mediterranean fruit fly, Ceratitis capitata in various concentrations (0.1, 0.3, 0.5 and 1.5 mg) prior to irradiation in order to obtain fully competent males. The produced full grown pupae were exposed to gamma rays at a dose rate of 90 Gy. Biological assessment of two E-Selen concentrations 0.3 and 0.5 mg were found to ameliorate the fitness of the sterile insects as well as to increase significantly most of their amino acids content. The study of the PCR patterns of normal and irradiated C. capitata undertaken or not different doses of E-Selen prior to irradiation and contained in the larval diets induced some modifications to the DNA profiles. The appearance of some new bands and disappearance of others were frequently encountered during this investigation. The appearance of bands was attributed to a repair mechanism that occurs in the irradiated DNA. However, the similarity in the DNA patterns of the homogenate pupal of C. capitata was due to the irradiation-induced damage may be in genome regions other than the regions of study

Vibrational spectra of monouranates and uranium hydroxides as reaction products of alkali with uranyl nitrate

International Nuclear Information System (INIS)

Komyak, A.I.; Umrejko, D.S.; Posledovich, M.R.

2013-01-01

Vibrational (IR absorption and Raman scattering) spectra for the reaction products of uranyl nitrate hexahydrate with NaOH and KOH have been studied. As a result of exchange reactions, the uranyl-ion coordinated nitrate groups are completely replaced by hydroxyl ions and various uranium and uranyl oxides or hydrates are formed. An analysis of the vibrations has been performed in terms of the frequencies of a free or coordinated nitrate group; comparison with the vibrations of the well-known uranium oxides and of the uranyl group UO 2 2+ has been carried out. Vibrational spectra of a free nitrate group are characterized by four vibrational frequencies 1050, 724, 850, and 1380 cm -1 , among which the frequencies at 724 and 1380 cm -1 are doubly degenerate and attributed to E’ symmetry of the point group D 3h . When this group is uranium coordinated, its symmetry level is lowered to C 2v , all vibrations of this group being active both in Raman and IR spectra. The doubly degenerate vibrations are exhibited as two bands and a frequency of the out-of-plane vibration is lowered to 815 cm -1 . (authors)

Method of separation of uranium from contaminating ions in an aqueous feed liquid containing uranyl ions

International Nuclear Information System (INIS)

Sundar, P.S.; Elikan, L.; Lyon, W.L.

1975-01-01

A coupled cationic/anionic method for the separation of uranium from contaminated aqueous solutions which contain uranyl ions is proposed. The fluid is extracted using an organic solvent containing a reagent which, together with the uranyl ions, forms a soluble aggregate in that solvent. As an example, 0.1 - 1 Mol/l Di-2-ethyl-hexyl-phosphorous acid in kerosene is mentioned. The organic solvent is then treated with a sealing liquid (volume ratio 20 - 35). For separation, an aqueous carbonate solution or a sulfuric acid solution can be used; the most favorable pH-values and concentrations for both cases are mentioned. The U +4 -ion at the sulfuric acid separation is subsequently oxidized to the uranyl ion with air. In each case, an extraction with an amine follows; after that, the amine is separated using an ammonium-carbonate solution and the uranium aggregate is precipitated, for example as ammonium uranyl tricarbonate, and then further processed to uranium oxide. The solvents and fluids used are led back in closed circuit; a flow diagram is given. (UWI) [de

Preparation and physicochemical characterization of anionic uranyl. beta. -ketoenolates

Energy Technology Data Exchange (ETDEWEB)

Marangoni, G; Paolucci, G [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi; Graziani, R; Celon, E

1978-01-01

New classes of anionic uranyl ..beta..-ketoenolates of formula (UO/sub 2/L/sub 2/X)/sup -/ (where L = 1,3-diphenylpropane-1,3-dionate (dppd), 4,4,4-trifluoro-1-phenylbutane-1,3-dionate (tfpbd), or 1-phenylbutane-1,3-dionate (pbd); X = Cl/sup -/, Br/sup -/, I/sup -/, (NO/sub 3/)/sup -/, (O/sub 2/CMe)/sup -/, or (NCS)/sup -/) and (L/sub 2/O/sub 2/U(..mu..-X) UO/sub 2/L/sub 2/)/sup -/ (where X = F/sup -/, and also Cl/sup -/ only in the case of L = dppd) have been synthesized and characterized by a number of physical measurements. The different ability of the various anionic ligands to enter into the co-ordination sphere of the uranyl ion, their potentially different bonding modes, and the possible correlations between physical parameters and the nature of either the chelate substituents or the anionic ligand are discussed.

Uranyl(VI) luminescence spectroscopy at elevated temperatures

Energy Technology Data Exchange (ETDEWEB)

Steudtner, Robin; Franzen, Carola; Brendler, Vinzenz [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Div. Surface Processes; Haubitz, Toni [Brandenburg Univ. of Technology, Cottbus-Senftenberg (Germany)

2016-07-01

We studied the influence of temperature and ionic strength on the luminescence characteristics (band position, decay time and intensity) of the free uranyl ion (UO{sub 2}{sup 2+}) in acidic aqueous solution. Under the chosen conditions an increasing temperature reduced both intensity and luminescence decay time of the UO{sub 2}{sup 2+} luminescence, but the individual U(VI) emission bands did not change.

Kinetic studies of uranyl ion adsorption on acrylonitrile (AN)/polyethylene glycol (PEG) interpenetrating networks (IPN)

International Nuclear Information System (INIS)

Aycik, G.A.; Gurellier, R.

2004-01-01

Full text: The kinetics of the adsorption of uranyl ions on amidoximated acrylonitrile (AN)/ polyethylene glycol (PEG) interpenetrating network (IPNs) from aqueous solutions was studied as a function of time and temperature. The IPNs were prepared by irradiation initiated gamma polymerisation using Co-60 gamma source. Adsorption capacities were performed for definite uranyl ion concentrations of 1x10 -2 M and at four different temperatures as 290K, 298K, 308K and 318K by gamma spectrometer. Adsorption time was increased from zero to 48 hours. The results indicate that adsorption capacity increases linearly with increasing temperature. Temperature and agitation hardly influence equilibrium and kinetics and decreasing of temperature results in a slightly greater time to reach equilibrium. The adsorption of uranyl ions has been studied in a multi step mechanism processes thus comparing chemical sorption and diffusion sorption processes. The experimental data was analysed using various kinetic models to determine the best-fit equation for the adsorption mechanisms. However, it was shown that all models, in general according to the reaction time and uranyl ion concentration in the solution, could describe the adsorption of uranyl ion onto amidoximated IPN, the adsorption kinetics was best described by zeroth order and intraparticle diffusion model whereas that of in increasing time by pseudo first and pseudo second order response respectively. External-intraparticle diffusion and zeroth order process in the IPN structure is proposed as a mass transfer mechanism and the results indicate a diffusion-controlled process. The Mean Activation Energy Of Uranyl Ions Adsorption Was Found As 4,1 Kj/Mole By Using Arrhenius Equation. The Rate Constant, The Equilibrium Adsorption Capacity And The Initial Adsorption Rate Were Calculated For All Models At Each Temperature. Kinetic Parameters Of All Models And The Normalized Standard Deviations Between The Measured And Predicted

A new synthetic methodology for the preparation of biocompatible and organo-soluble barbituric- and thiobarbituric acid based chitosan derivatives for biomedical applications

Energy Technology Data Exchange (ETDEWEB)

Shahzad, Sohail [Interdisciplinary Research Center in Biomedical Materials, COMSATS Institute of Information Technology, Lahore 54000 (Pakistan); Department of Chemistry, The Islamia University of Bahawalpur, Bahawalpur 63100 (Pakistan); Shahzadi, Lubna [Interdisciplinary Research Center in Biomedical Materials, COMSATS Institute of Information Technology, Lahore 54000 (Pakistan); Mahmood, Nasir [Department of Allied Health Sciences and Chemical Pathology, Department of Human Genetics and Molecular Biology, University of Health Sciences, Lahore (Pakistan); Siddiqi, Saadat Anwar [Interdisciplinary Research Center in Biomedical Materials, COMSATS Institute of Information Technology, Lahore 54000 (Pakistan); Rauf, Abdul [Department of Chemistry, The Islamia University of Bahawalpur, Bahawalpur 63100 (Pakistan); Manzoor, Faisal; Chaudhry, Aqif Anwar [Interdisciplinary Research Center in Biomedical Materials, COMSATS Institute of Information Technology, Lahore 54000 (Pakistan); Rehman, Ihtesham ur [Interdisciplinary Research Center in Biomedical Materials, COMSATS Institute of Information Technology, Lahore 54000 (Pakistan); Department of Materials Science and Engineering, The Kroto Research Institute, The University of Sheffield, North Campus, Broad Lane, Sheffield, S3 7HQ (United Kingdom); Yar, Muhammad, E-mail: drmyar@ciitlahore.edu.pk [Interdisciplinary Research Center in Biomedical Materials, COMSATS Institute of Information Technology, Lahore 54000 (Pakistan)

2016-09-01

Chitosan's poor solubility especially in organic solvents limits its use with other organo-soluble polymers; however such combinations are highly required to tailor their properties for specific biomedical applications. This paper describes the development of a new synthetic methodology for the synthesis of organo-soluble chitosan derivatives. These derivatives were synthesized from chitosan (CS), triethyl orthoformate and barbituric or thiobarbituric acid in the presence of 2-butannol. The chemical interactions and new functional motifs in the synthesized CS derivatives were evaluated by FTIR, DSC/TGA, UV/VIS, XRD and {sup 1}H NMR spectroscopy. A cytotoxicity investigation for these materials was performed by cell culture method using VERO cell line and all the synthesized derivatives were found to be non-toxic. The solubility analysis showed that these derivatives were readily soluble in organic solvents including DMSO and DMF. Their potential to use with organo-soluble commercially available polymers was exploited by electrospinning; the synthesized derivatives in combination with polycaprolactone delivered nanofibrous membranes. - Highlights: • Development of a new synthetic methodology • Synthesis of organo-soluble chitosan (CS) derivatives • VERO cells proliferation • Nanofibrous membranes from the synthesized chitosan derivatives and polycaprolactone.

Observation of Possible Lava Tube Skylights by SELENE cameras

Science.gov (United States)

Haruyama, Junichi; Hiesinger, Harald; van der Bogert, Carolyn

We have discovered three deep hole-structures on the Moon in the Terrain Camera and Multi-band Imager on the SELENE. These holes are large depth to diameter ratios: Marius Hills Hole (MHH) is 65 m in diameter and 88-90 m in depth, Mare Tranquillitatis Hole (MTH) is 120 x 110 m in diameter and 180 m in depth, and Mare Ingenii Hole (MIH) is 140 x 110 m in diameter and deeper than 90 m. No volcanic material from the holes nor dike-relating pit craters is seen around the holes. They are possible lava tube skylights. These holes and possibly connected tubes have a lot of scientific interests and high potentialities as lunar bases.

Determination of free nitric acid in uranyl nitrate solution

International Nuclear Information System (INIS)

Mayankutty, P.C.; Ravi, S.; Nadkarni, M.N.

1981-01-01

Potentiometric titration of uranyl nitrate solution with sodium hydroxide exhibits two peaks. The first peak characterises the following reaction, UO 2 (C 2 O 4 )+NaOH Na[UO 2 (C 2 O 4 )(OH)]. This reaction, indicating the partial hydrolysis of uranyl oxalate complex, appears to be complete at pH9. If the titration is carried out to this end-point pH, the total alkali consumed can be equated to the sum of uranium content and the free acidity present in the sample volume. Based on this, a method was standardised to determine the free acidity in uranyl nitrate solution. The sample, taken in a solution of potassium oxalate previously adjusted to pH9, is titrated to this pH with standard sodium hydroxide. The free acidity in the sample can be computed by subtracting the alkali reacted with uranium from the total alkali consumed. Analyses of several synthetic samples containing uranium and nitric acid in a wide range of combinations indicate that the free acidity can be accurately determined by this method, if uranium concentration in the sample is known. The results are compared to those obtained by two other widely used methods, viz., (i) titration of pH7 in the presence of neutral potassium oxalate to suppress hydrolysis and (ii) separation of hydrolyzable ions on a cationic resin and alkali titration of the free acid released. The advantages of and the precision obtained with the present method over the above two methods are discussed. (author)

Effect of surfactant alkyl chain length on the dispersion, and thermal and dynamic mechanical properties of LDPE/organo-LDH composites

Directory of Open Access Journals (Sweden)

2011-05-01

Full Text Available Low density polyethylene/layered double hydroxide (LDH composites were prepared via melt compounding using different kinds of organo-LDHs and polyethylene-grafted maleic anhydride as the compatibilizer. The organo-LDHs were successfully prepared by converting a commercial MgAl-carbonate LDH into a MgAl-nitrate LDH, which was later modified by anion exchange with linear and branched sodium alkyl sulfates having different alkyl chain lengths (nc = 6, 12 and 20. It was observed that, depending on the size of the surfactant alkyl chain, different degrees of polymer chain intercalation were achieved, which is a function of the interlayer distance of the organo-LDHs, of the packing level of the alkyl chains, and of the different interaction levels between the surfactant and the polymer chains. In particular, when the number of carbon atoms of the surfactant alkyl chain is larger than 12, the intercalation of polymer chains in the interlayer space and depression of the formation of large aggregates of organo-LDH platelets are favored. A remarkable improvement of the thermal-oxidative degradation was evidenced for all of the composites; whereas only a slight increase of the crystallization temperature and no significant changes of both melting temperature and degree of crystallinity were achieved. By thermodynamic mechanical analysis, it was evidenced that a softening of the matrix is may be due to the plasticizing effect of the surfactant.

Electrochemical studies on the reduction of uranyl ions in nitric acid-hydrazine media at platinum electrode

International Nuclear Information System (INIS)

Mishra, Satyabrata; Sini, K.; Mallika, C.; Kamachi Mudali, U.; Jagadeeswara Rao, Ch.

2015-01-01

Production of uranous nitrate with good conversion efficiency is one of the major steps in the aqueous reprocessing of spent fuels of nuclear reactors, as U(IV) is used for the separation of Pu from U by the selective reduction of Pu(IV) into practically non-extractable Pu(III) in aqueous streams. Electro-reduction of uranyl ions has the advantage of not introducing corrosive chemicals into the process stream. High current efficiency with maximum conversion of U(VI) to U(IV) can be achieved in continuous as well as batch mode electro-reduction, if the process is voltage-controlled rather than current controlled. As potentiostatic studies reveal the mechanism of reduction of uranyl ions in potential controlled electrolysis, the reduction behavior of uranyl ions (UO 2 2+ ) in nitric acid and nitric acid-hydrazine media were investigated by Cyclic Voltammetric (CV) and Chronopotentiometric (CP) techniques using platinum working electrode at 298 K. Heterogeneous electron transfer rate constant (ks) for uranyl reduction was estimated at a very low concentration of nitric acid (0.05 M) using Klinger and Kochi equation. Values of the diffusion coefficients were determined as a function of acidity with and without hydrazine. Reduction of uranyl ions was found to be under kinetic as well as diffusion control when the concentration of nitric acid was 0.05 M and in the absence of hydrazine. However, as the acidity of the supporting electrolyte increased, the reduction was purely under kinetic control. (author)

Kinetic analysis of laser induced phosphorescence in uranyl phosphate for improved analytical measurements

International Nuclear Information System (INIS)

Bushaw, B.A.

1983-10-01

Pulsed dye-laser excitation with multichannel scaler photon counting is used to obtain time resolved emission spectra of uranyl ions in aqueous solution. Kinetic analysis of this data corrects for matrix quenching and temperature effects which reduce the quantum yield of the uranyl ion luminescence. The method gives accurate measurements without separative prechemistry or the use of internal standards. Detection limits of one part-per-trillion (pptr) have been demonstrated, and in samples with concentrations greater than 100 pptr, relative standard deviations of less than 3% are achieved routinely

First start-up of nuclear criticality safety experiment facility for uranyl nitrate solution

International Nuclear Information System (INIS)

Zhu Qingfu; Shi Yongqian; Shen Leisheng; Hu Dingsheng; Zhao Shouzhi; He Tao; Sun Zheng; Lin Shenghuo; Yao Shigui

2005-01-01

The uranyl nitrate solution experiment facility for the research on nuclear criticality safety is described. The nuclear fuel loading steps in the first start-up for water-reflected core are presented. During the experiments, the critical volume of uranyl nitrate solution was determined as 20479.62 mL with count rate inverse extrapolation method, reactivity interpolation method, and steady power method. By calculation, critical mass of 235 U was derived as 1579.184 g from experimental data. The worth of control rods was also calibrated in the first start-up of the facility. (authors)

Mechanism of the reduction of hexavalent chromium by organo-montmorillonite supported iron nanoparticles

International Nuclear Information System (INIS)

Wu, Pingxiao; Li, Shuzhen; Ju, Liting; Zhu, Nengwu; Wu, Jinhua; Li, Ping; Dang, Zhi

2012-01-01

Highlights: ► Organo-montmorillonite supported iron nanoparticles were found to be more efficient in the removal of Cr(VI) than unsupported iron nanoparticles. ► The iron nanoparticles were accommodated by the sectional structure of the clay minerals which were helpful to protect the nanoparticles from aggregating. ► XPS and XANES provided some direct information about the reduction mechanisms. ► The structure of the supported iron nanoparticles was stable in the reaction with Cr(VI). - Abstract: Iron nanoparticles exhibit greater reactivity than micro-sized Fe 0 , and they impart advantages for groundwater remediation. In this paper, supported iron nanoparticles were synthesized to further enhance the speed and efficiency of remediation. Natural montmorillonite and organo-montmorillonite were chosen as supporting materials. The capacity of supported iron nanoparticles was evaluated, compared to unsupported iron nanoparticles, for the reduction of aqueous Cr(VI). The reduction of Cr(VI) was much greater with organo-montmorillonite supported iron nanoparticles and fitted the pseudo-second order equation better. With a dose at 0.47 g/L, a total removal capacity of 106 mg Cr/g Fe 0 was obtained. Other factors that affect the efficiency of Cr(VI) removal, such as pH values, the initial Cr(VI) concentration and storage time of nanoparticles were investigated. X-ray photoelectron spectrometry (XPS) and X-ray absorption near edge structure (XANES) were used to figure out the mechanism of the removal of Cr(VI). XPS indicated that the Cr(VI) bound to the particle surface was completely reduced to Cr(III) under a range of conditions. XANES confirmed that the Cr(VI) reacted with iron nanoparticles was completely reduced to Cr(III).

Diffusion, sorption, and retardation processes of anions in bentonite and organo-bentonites for multibarrier systems

Science.gov (United States)

Schampera, Birgit; Dultz, Stefan

2013-04-01

The low permeability, high cation exchange capacity (CEC) and plasticity of bentonites favor their use in multibarrier systems of waste deposits [1]. Bentonites have a high CEC but their ability to sorb anions is very low. There is, however, need for retardation of anions and organic pollutants in many applications. Bentonites, modified with certain organic cations, have the capacity to sorb anions and non-polar organic compounds in addition to cations. Investigations on organically modified clays address a wide variety of applications including immobilization of pollutants in contaminated soils, waste water treatment and in situ placement for the protection of ground water [2]. Many experiments on anion and cation sorption of organo-clays were conducted in the batch mode which does not reflect solid-liquid ratios and material densities in barrier systems. Diffusion experiments on compacted clays allow the evaluation of transport processes and sorption of pollutants at conditions relevant for repositories. For organo-clays only few diffusion studies are published e.g. [3] measured the diffusion of tritium and [4] the diffusion of H2O in bentonite and organo-bentonites. The organic cation hexadecylpyridinium (HDPy) was added to Wyoming bentonite (MX-80) in amounts corresponding to 2-400 % of the CEC. The uptake of organic cations was determined by the C-content, XRD and IR-spectroscopy. Wettability was analyzed by the contact angle. Physical, chemical and mineralogical properties of clays were characterized. Diffusion experiments were carried out in situ in a cell attached to the ATR-unit of a FTIR-spectrometer. For H2O-diffusion the compacted organo-clays are saturated first with D2O, afterwards H2O is supplied to the surface at the top of the clay platelet. Anion-diffusion was conducted with NO3--solution instead of H2O only having characteristic IR band positions at 1350 cm-1. Three different concentrations (0.25M, 0.5M and 1M) were used. Additional batch

From zinc selenate to zinc selenide nano structures synthesized by reduction process

International Nuclear Information System (INIS)

Hutagalung, S.D.; Eng, S.T.; Ahmad, Z.A.; Ishak Mat; Yussof Wahab

2009-01-01

One-dimensional nano structure materials are very attractive because of their electronic and optical properties depending on their size. It is well known that properties of material can be tuned by reducing size to nano scale because at the small sizes, that they behave differently with its bulk materials and the band gap will control by the size. The tunability of the band gap makes nano structured materials useful for many applications. As one of the wide band gaps semiconductor compounds, zinc selenide (ZnSe) nano structures (nanoparticles, nano wires, nano rods) have received much attention for the application in optoelectronic devices, such as blue laser diode, light emitting diodes, solar cells and IR optical windows. In this study, ZnSe nano structures have been synthesized by reduction process of zinc selenate using hydrazine hydrate (N 2 H 4 .2H 2 O). The reductive agent of hydrazine hydrate was added to the starting materials of zinc selenate were heat treated at 500 degree Celsius for 1 hour under argon flow to form one-dimensional nano structures. The SEM and TEM images show the formation of nano composite-like structure, which some small nano bar and nano pellets stick to the rod. The x-ray diffraction and elemental composition analysis confirm the formation of mixture zinc oxide and zinc selenide phases. (author)

MODELING THE INTERACTION OF AGROCHEMICALS WITH ENVIRONMENTAL SURFACES: PESTICIDES ON RUTILE AND ORGANO-RUTILE SURFACES

Science.gov (United States)

Non-bonded interactions between model pesticides and organo-mineral surfaces have been studied using molecular mechanical conformational calculations and molecular dynamics simulations. The minimum energy conformations and relative binding energies for the interaction of atrazine...

DFT study of uranyl peroxo complexes with H2O, F-, OH-, CO3(2-), and NO3(-).

Science.gov (United States)

Odoh, Samuel O; Schreckenbach, Georg

2013-05-06

The structural and electronic properties of monoperoxo and diperoxo uranyl complexes with aquo, fluoride, hydroxo, carbonate, and nitrate ligands have been studied using scalar relativistic density functional theory (DFT). Only the complexes in which the peroxo ligands are coordinated to the uranyl moiety in a bidentate mode were considered. The calculated binding energies confirm that the affinity of the peroxo ligand for the uranyl group far exceeds that of the F(-), OH(-), CO3(2-), NO3(-), and H2O ligands. The formation of the monoperoxo complexes from UO2(H2O)5(2+) and HO2(-) were found to be exothermic in solution. In contrast, the formation of the monouranyl-diperoxo, UO2(O2)2X2(4-) or UO2(O2)2X(4-/3-) (where X is any of F(-), OH(-), CO3(2-), or NO3(-)), complexes were all found to be endothermic in aqueous solution. This suggests that the monoperoxo species are the terminal monouranyl peroxo complexes in solution, in agreement with recent experimental work. Overall, we find that the properties of the uranyl-peroxo complexes conform to well-known trends: the coordination of the peroxo ligand weakens the U-O(yl) bonds, stabilizes the σ(d) orbitals and causes a mixing between the uranyl π- and peroxo σ- and π-orbitals. The weakening of the U-O(yl) bonds upon peroxide coordination results in uranyl stretching vibrational frequencies that are much lower than those obtained after the coordination of carbonato or hydroxo ligands.

Crystal structure of the uranyl-oxide mineral rameauite

Czech Academy of Sciences Publication Activity Database

Plášil, Jakub; Škoda, R.; Čejka, J.; Bourgoin, V.; Boulliard, J.C.

2016-01-01

Roč. 28, č. 5 (2016), s. 959-967 ISSN 0935-1221 R&D Projects: GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : rameauite * uranyl-oxide hydroxy-hydrate * crystal structure * Raman spectrum Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.362, year: 2016

Synthesis of phosphorylated calix[4]arene derivatives for the design of solid phases immobilizing uranyl cations

International Nuclear Information System (INIS)

Maroun, E.B.; Hagege, A.; Asfari, Z.; Basset, CH.; Quemeneur, E.; Vidaud, C.

2009-01-01

With the aim of developing supports for uranyl cations immobilisation, new 1, 3-alternate calix[4]arenes bearing both phosphonic acid functions as chelating sites and N-succinimide-4-oxa-butyrate as the anchoring arm were synthesised in good yields. The coupling of such calixarenes to a gel was performed and a successful immobilisation of uranyl cations was obtained. (authors)

Synthesis of phosphorylated calix[4]arene derivatives for the design of solid phases immobilizing uranyl cations

Energy Technology Data Exchange (ETDEWEB)

Maroun, E.B.; Hagege, A.; Asfari, Z. [Laboratoire de Chimie Analytique et Minerale, UMR 7178 ULP/CNRS/IN2P3 LC4, ECPM, Strasbourg Cedex (France); Basset, CH.; Quemeneur, E.; Vidaud, C. [CEA IBEB, SBTN, Centre de Marcoule, Bagnols-sur-Ceze (France)

2009-07-01

With the aim of developing supports for uranyl cations immobilisation, new 1, 3-alternate calix[4]arenes bearing both phosphonic acid functions as chelating sites and N-succinimide-4-oxa-butyrate as the anchoring arm were synthesised in good yields. The coupling of such calixarenes to a gel was performed and a successful immobilisation of uranyl cations was obtained. (authors)

The bare uranyl(2+) ion, UO22+

International Nuclear Information System (INIS)

Cornehl, H.H.; Heinemann, C.; Marcalo, J.; Pires de Matos, A.; Schwarz, H.

1996-01-01

Ion-molecule reactions between U 2+ and oxygen donors or charge-stripping collisions between singly charged UO 2 2 ions and O 2 collision partners generate uranyl(2+) ions in the gas phase. These do not readily dissociate into singly charged fragments. The standard enthalpy of formation for UO 2 2+ is estimated to be 371±60 kcal mol -1 , in accord with the results of ab initio calculations. (orig.)

Uptake and specification of selenium in garlic cultivated in soil amended with symbiotic fungi (mycorrhiza) and selenate

NARCIS (Netherlands)

Larsen, E.H.; Lobinski, R.; Burger-Meijer, K.; Hansen, M.; Ruzik, R.; Mazurowska, L.; Rasmussen, P.H.; Sloth, J.J.; Scholten, O.E.; Kik, C.

2006-01-01

The scope of the work was to investigate the influence of selenate fertilisation and the addition of symbiotic fungi (mycorrhiza) to soil on selenium and selenium species concentrations in garlic. The selenium species were extracted from garlic cultivated in experimental plots by proteolytic

Synthesis and crystal structure of a new neodymium(III) selenate-selenite: Nd2(SeO4)(SeO3)2(H2O)2

International Nuclear Information System (INIS)

Feng Meiling; Mao Jianggao

2005-01-01

The title new neodymium(III) selenate-selenite was obtained by hydrothermal reactions of neodymium(III) oxide, H 2 SeO 4 and 1,10-phenanthroline at 140 o C. Its structure was established by single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic space group C2/c with cell parameters of a = 12.258(2) A, b 7.1024(15) A, c = 13.391(3) A, β = 104.250(2) o . The structure of Nd 2 (SeO 4 )(SeO 3 ) 2 (H 2 O) 2 is isomorphous with that of Er 2 (SeO 4 )(SeO 3 ) 2 (H 2 O) 2 , which was refined in the monoclinic space group C2 with the disordered selenate group. It features an ordered 3D network with channels along b-axis. The selenate or selenite groups alone can form a 2D layer with the Nd(III) ions. IR spectrum, TGA and luminescent studies have also been performed

Photophysics of the excited uranyl ion in aqueous solutions

International Nuclear Information System (INIS)

Formosinho, S.J.; Miguel, M. da G.M.

1985-01-01

The effect of the micelles of Triton X-100 on the biexponential decay of (UO 2 2+ )* has been investigated. Data are analysed in terms of a reversible crossing mechanism for the decay. Azulene fluorescence quenching and 13 C n.m.r. studies strongly suggest that uranyl ions are able to penetrate deep inside the micelle core. Micelle quenching for the reversible decay of (UO 2 2+ )* occurs in the interior (ksub(q) = 3 x 10 10 dm 3 mol -1 s -1 ) and at the surface (Ksub(q) = 1.5 x 10 9 mol -1 dm 3 s -1 ) of the micelles. The latter process has a rate virtually identical to that for the free surfactant molecules. Penetration of (UO 2 2+ )* inside the non-polar regions of the micelle core increases solvent exchange rates by ca. two orders of magnitude. Uranyl-ion excimers are formed in occupied micelles. The quenching processes decrease strongly for these species because excimers do not penetrate the micelles. (author)

Colorimetric peroxidase mimetic assay for uranyl detection in sea water

KAUST Repository

Zhang, Dingyuan; Chen, Zhuo; Omar, Haneen; Deng, Lin; Khashab, Niveen M.

2015-01-01

Uranyl (UO2 2+) is a form of uranium in aqueous solution that represents the greatest risk to human health because of its bioavailability. Different sensing techniques have been used with very sensitive detection limits especially the recently

Determination of Proteinaceous Selenocysteine in Selenized Yeast

Directory of Open Access Journals (Sweden)

Katarzyna Bierla

2018-02-01

Full Text Available A method for the quantitation of proteinaceous selenocysteine (SeCys in Se-rich yeast was developed. The method is based on the reduction of the Se-Se and S-Se bridges with dithiotretiol, derivatization with iodoacetamide (carbamidomethylation, followed by HPLC-ICP MS. The chromatographic conditions were optimized for the total recovery of the proteinaceous selenocysteine, the minimum number of peaks in the chromatogram (reduction of derivatization products of other Se-species present and the baseline separation. A typical chromatogram of a proteolytic digest of selenized yeast protein consisted of up to five peaks (including SeMet, carbamidomethylated (CAM-SeCys, and Se(CAM2 identified by retention time matching with available standards and electrospray MS. Inorganic selenium non-specifically attached to proteins and selenomethionine could be quantified (in the form of Se(CAM2 along with SeCys. Selenocysteine, selenomethionine, inorganic selenium, and the water soluble-metabolite fraction accounted for the totality of selenium species in Se-rich yeast.

[UO{sub 2}Cl{sub 2}(phen){sub 2}], a simple uranium(VI) compound with a significantly bent uranyl unit (phen=1,10-phenanthroline)

Energy Technology Data Exchange (ETDEWEB)

Schoene, Sebastian; Radoske, Thomas; Maerz, Juliane; Stumpf, Thorsten; Patzschke, Michael; Ikeda-Ohno, Atsushi [Helmholtz-Zentrum Dresden-Rossendorf (HZDR), Institute of Resource Ecology, Dresden (Germany)

2017-10-04

A simple synthesis based on UO{sub 2}Cl{sub 2}.n H{sub 2}O and 1,10-phenanthroline (phen) resulted in the formation of a new uranyl(VI) complex [UO{sub 2}Cl{sub 2}(phen){sub 2}] (1), revealing a unique dodecadeltahedron coordination geometry around the uranium center with significant bending of the robust linear arrangement of the uranyl (O-U-O) unit. Quantum chemical calculations on complex 1 indicated that the weak but distinct interactions between the uranyl oxygens and the adjacent hydrogens of phen molecules play an important role in forming the dodecadeltahedron geometry that fits to the crystal structure of 1, resulting in the bending the uranyl unit. The uranyl oxygens in 1 are anticipated to be activated as compared with those in other linear uranyl(VI) compounds. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Enantioselective organo-photocatalysis mediated by atropisomeric thiourea derivatives.

Science.gov (United States)

Vallavoju, Nandini; Selvakumar, Sermadurai; Jockusch, Steffen; Sibi, Mukund P; Sivaguru, Jayaraman

2014-05-26

Can photocatalysis be performed without electron or energy transfer? To address this, organo-photocatalysts that are based on atropisomeric thioureas and display lower excited-state energies than the reactive substrates have been developed. These photocatalysts were found to be efficient in promoting the [2+2] photocycloaddition of 4-alkenyl-substituted coumarins, which led to the corresponding products with high enantioselectivity (77-96% ee) at low catalyst loading (1-10 mol%). The photocatalytic cycle proceeds by energy sharing via the formation of both static and dynamic complexes (exciplex formation), which is aided by hydrogen bonding. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of the extractive capacity of para-tert butyl calix[8]arene octa-phosphinoylated towards uranyl ions from an aqueous-acidic-salty medium

International Nuclear Information System (INIS)

Serrano V, E. C.

2011-01-01

The extraction properties of octa-phosphinoylated para-tert butyl calix[8]arene (prepared in the laboratory) in chloroform towards uranyl ions from an aqueous-acidic-salty medium (HNO 3 -3.5 NaNO 3 ) containing uranyl nitrate salt, was investigated. Two spectroscopic techniques UV/Vis and Luminescence were used for this study. The latter permitted analyze the fluorescence from the uranyl ions influenced by the surrounding medium. Both permitted to learn about the power of this calixarene as extractant towards the mentioned ions. Its extraction ability or capability using this calixarene at 5.91 x 10 -4 M towards the uranyl ions was 400% as determined by UV/Vis while fluorescence revealed 100% of uranyl ion extraction. A closed analysis of the results obtained by using these techniques revealed that the stoichiometry of the main extracted species was 1calixarene:2 uranyl ions. The loading capacity of the calixarene ligand towards the uranyl ions was also investigated using both techniques. UV/Vis resulted to be inadequate for quantifying exactly the loading capacity of the calixarene whereas luminescence was excellent indeed, using a 5.91 x 10 -4 M calixarene concentration, its loading capacity was 0.157 M of free uranyl ions from 0.161 M of uranyl ions present in the aqueous-acidic-salty medium. The extracts from the ability and capacity studies were concentrated to dryness, purified and the dried extracts were analyzed by infrared and neutron activation analysis. By these techniques it was demonstrated that during the extraction of the uranyl ions by the calixarene ligand they form thermodynamically and kinetically stable complexes, since in the solid state, the 1:2, calixarene; uranyl ions stoichiometry was kept with the minimum formula: (UO 2 ) 2 B 8 bL 8 (NO 3 ) 4 (H 2 O) 4 CHCl 3 (CH 3 OH) 3 the methanol molecules come from its purification. It is proposed that B 8 bL 8 calixarene in chloroform medium is a good extractant for the treatment of nuclear wastes or

An unprecedented two-fold nested super-polyrotaxane: sulfate-directed hierarchical polythreading assembly of uranyl polyrotaxane moieties

Energy Technology Data Exchange (ETDEWEB)

Mei, Lei; Wu, Qun-yan; Yuan, Li-yong; Wang, Lin; An, Shu-wen; Xie, Zhen-ni; Hu, Kong-qiu; Shi, Wei-qun [Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing (China); Chai, Zhi-fang [Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing (China); School of Radiological and Interdisciplinary Sciences and Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, Soochow University, Suzhou (China); Burns, Peter C. [Department of Chemistry and Biochemistry, University of Notre Dame, IN (United States)

2016-08-01

The hierarchical assembly of well-organized submoieties could lead to more complicated superstructures with intriguing properties. We describe herein an unprecedented polyrotaxane polythreading framework containing a two-fold nested super-polyrotaxane substructure, which was synthesized through a uranyl-directed hierarchical polythreading assembly of one-dimensional polyrotaxane chains and two-dimensional polyrotaxane networks. This special assembly mode actually affords a new way of supramolecular chemistry instead of covalently linked bulky stoppers to construct stable interlocked rotaxane moieties. An investigation of the synthesis condition shows that sulfate can assume a vital role in mediating the formation of different uranyl species, especially the unique trinuclear uranyl moiety [(UO{sub 2}){sub 3}O(OH){sub 2}]{sup 2+}, involving a notable bent [O=U=O] bond with a bond angle of 172.0(9) . Detailed analysis of the coordination features, the thermal stability as well as a fluorescence, and electrochemical characterization demonstrate that the uniqueness of this super-polyrotaxane structure is mainly closely related to the trinuclear uranyl moiety, which is confirmed by quantum chemical calculations. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Optical and structural properties of FeSe2 thin films obtained by selenization of sprayed amorphous iron oxide films

International Nuclear Information System (INIS)

Ouertani, B.; Ouerfelli, J.; Saadoun, M.; Zribi, M.; Rabha, M.Ben; Bessais, B.; Ezzaouia, H.

2006-01-01

We report in this work the optical and structural properties of iron diselenide films (FeSe 2 ) obtained by selenization under vacuum of amorphous iron oxide films predeposited by spray pyrolysis. The structure of the FeSe 2 films was investigated by scanning electron microscopy (SEM), microprobe analyses, atomic force microscopy (AFM) and X-ray diffraction (XRD). XRD and micro-probe analyses showed that FeSe 2 as well as FeSe 2-x phases begin to appear at a selenization temperature of 500 deg. C. As the selenization temperature rises, the iron diselenide films become more stoichiometric with a dominance of the FeSe 2 phase. At 550 deg. C, a single FeSe 2 phase having good crystallinity was obtained. At 600 deg. C, two phases were detected: the major one corresponds to Fe 3 O 4 , and the minor one to FeSe 2 . SEM surface views show that FeSe 2 films have granular structure with small spherical crystallites. However, layered and clustered FeSe 2 films were found, respectively, at 550 deg. C and 600 deg. C. Absorption measurements show that iron diselenide films have a direct and an indirect gaps of about 1.03 eV and 0.3 eV, which were suggested to be due to the stoichiometric FeSe 2 phase and to a Fe-rich non-stoichiometric phase, respectively

Novel two-dimensional uranyl-organic assemblages in the citrate and D(-)-citramalate families

International Nuclear Information System (INIS)

Thuery, P.

2008-01-01

Uranyl nitrate reacts with D(-)-citramalic acid (H(3)citml) under mild hydrothermal conditions to give the two-dimensional polymer [UO 2 (Hcitml)] 1, in which each ligand chelates one metal atom through its hydroxyl and alpha- carboxylate groups and binds to three others in monodentate fashion. The resulting neutral layers display isolated uranyl pentagonal bipyramidal polyhedra. Whereas citric acid (H(4)cit) has been shown previously to give various three- and mono-dimensional uranyl organic assemblages, complexation under hydrothermal conditions in the presence of either NaOH/NEt 4 Cl or pyridine yields the complexes [NEt 4 ] 2 [(UO 2 ) 3 (cit) 2 (H 2 O) 2 ]· 2H 2 O 2 and [Hpy] 2 )[(UO 2 ) 3 (cit)(Hcit)(OH)] 3, respectively, which both crystallize as two- dimensional frameworks. The layers are either planar and separated by the counter ions in 2 or corrugated and hydrogen bonded to one another in 3. In both 2 and 3, [UO 2 (cit)] 2 4- dimeric subunits with edge-sharing pentagonal bipyramidal uranium coordination polyhedra are present but, in both cases and in contrast with previous structures containing [UO 2 (Hcit)] 2 2- dimers, the carboxylate group not involved in the dimer formation is coordinated to another uranyl unit, which is part of either a centrosymmetric hexagonal bipyramidal bis-aquated group or a different, [(UO 2 ) 2 (Hcit)(OH)] dimer. These examples of two- dimensional assemblages further illustrate the variety of architectures which can be obtained with citric and related acids and the important structure-directing effects of the counter ions. (author)

Comparing uranyl sorption complexes on soil and reference clays

International Nuclear Information System (INIS)

Chisholm-Brause, C.J.; Berg, J.M.; Conradson, S.D.; Morris, D.E.; McKinley, J.P.; Zachara, J.M.

1993-01-01

Clay minerals and other components in natural soils may play a key role in limiting the mobility of uranium in the environment through the formation of sorption complexes. Reference clays are frequently used as models to study sorption processes because they have well-known chemical and physical properties, but they may differ chemically and morphologically from clays derived from natural soils. Therefore, inferences based on reference clay data have been questioned. The authors have used luminescence and x-ray absorption spectroscopies to characterize the sorption complexes of aqueous uranyl (UO 2 2+ ) species on two soil smectites from the Kenoma and Ringold formations, and compared these results to those obtained on reference smectite clays. The pH dependence of uptake suggests that the ratio of sorption on amphoteric edge sites is greater for the soil smectites than for reference clays such as Wyoming montmorillonite (SWy-1). The luminescence spectra for uranyl sorbed to the soil clays are very similar to those for uranyl sorbed principally to the edge sites of SWy-1. This observation supports the solution data suggesting that adsorption to amphoteric sites is a more important mechanism for soil clays. However, the spectral data indicate that the sorption complexes on natural and reference clays are quite similar. Furthermore, as with the reference clays, the authors have found that the chemistry of the solution plays a greater role in defining the sorption complex than does the clay matrix. Thus, if differences in surface properties are adequately taken into account, the reference clays may serve as useful analogs for soil clays in investigations of metal-ion sorption

Crystal field influence on vibration spectra: anhydrous uranyl chloride and dihydroxodiuranyl chloride tetrahydrate

International Nuclear Information System (INIS)

Perrin, Andre; Caillet, Paul

1976-01-01

Vibrational spectra of anhydrous uranyl chloride UO 2 Cl 2 and so called basic uranyl chloride: dihydroxodiuranyl chloride tetrahydrate /UO 2 (OH) 2 UO 2 /Cl 2 (H 2 O) 4 are reported. Factor group method analysis leads for the first time to complete and comprehensive interpretation of their spectra. Two extreme examples of crystal field influence on vibrational spectra are pointed out: for UO 2 Cl 2 , one is unable to explain spectra without taking into account all the elements of primitive crystalline cell, whilst for dihydroxodiuranyl dichloride tetrahydrate the crystal packing has very little effect on vibrational spectra [fr

Controlled deprotection and reorganization of uranyl oxo groups in a binuclear macrocyclic environment

International Nuclear Information System (INIS)

Jones, Guy M.; Arnold, Polly L.; Love, Jason B.

2012-01-01

Switching on uranium(V) reactivity: The silylated uranium(V) dioxo complex [(Me_3SiOUO)_2(L)_2] (A) is inert to oxidation, but after two-electron reduction to [(Me_3SiOUO)_2(L)]"2"- (1), it can be desilylated to form [OU(μ-O)_2UO(L)_2]"2"- (2) with reinstated uranyl character. Removal of the silyl group uncovers new redox and oxo rearrangement chemistry for uranium, thus reforming the uranyl motif and involving the U"V"I"/"V couple in dioxygen reduction. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Determination of uranium in uranyl nitrate solutions of nuclear grade quality - Gravimetric method

International Nuclear Information System (INIS)

1990-01-01

This international Standard specifies a precise and accurate gravimetric method for determining the uranium content in uranyl nitrate product solutions of nuclear grade quality at concentrations above 100 g/l of uranium. Non-volatile impurities influence the accuracy of the method. Uranyl nitrate is converted into uranium octoxide (U 3 O 8 ) by ignition in air to constant mass at 900 deg. C ± 10 deg. C. Calculation of the uranium content in the sample using a gravimetric conversion factor which depends on the isotopic composition of the uranium. The isotopic composition is determined by mass spectrometry

Interaction of aluminium(3) with uranyl ions in the course of joint hydrolysis

International Nuclear Information System (INIS)

Yusov, A.B.; Budantseva, N.A.; Fedoseev, A.M.; Astafurova, L.N.

2001-01-01

By means of spectrophotometry, luminescence and IR-spectroscopy one studied interaction of uranyl ions with Al 3+ ions in solutions at pH≥2 and in precipitates at pH≥5. It is shown that within 3-4 pH range the uranyl hydrolyzed forms interact with these of aluminium. Mixed hydroxoaquacomplexes are likely to be formed in solution with U:Al = 1:1 molar ratio. Large-size mixed polymers may be formed with pH increase. Varying of precipitation pH from 5 up to 14 does not minimize the importance of the oligomer mixed compounds for precipitation formation [ru

Effect of uranyl nitrate and free acid concentration in feed solution of gelation on UO2 kernel quality

International Nuclear Information System (INIS)

Masduki, B.; Wardaya; Widarmoko, A.

1996-01-01

An investigation on the effect of uranium and free nitric acid concentration of uranyl nitrate as feed of gelation process on quality of UO 2 kernel was done.The investigation is to look for some concentration of uranyl nitrate solutions those are optimum as feed for preparation of gelled UO 3 . Uranyl nitrate solution of various concentration of uranium (450; 500; 550; 600; 650; 700 g/l) and free nitric acid of (0.9; 1.0; 1.1 N) was made into feed solutions by adding urea and HMTA with mole ratio of urea/uranium and HMTA/uranium 2.1 and 2.0. The feed solutions were changed into spherical gelled UO 3 by dropping was done to get the optimum concentrations of uranyl nitrate solutions. The gelled UO 3 was soaked and washed with 2.5% ammonia solution for 17 hours, dried at 70 o C, calcined at 350 o C for 3 hours then reduced at 850 o C for 3 hours. At every step of the steps process the colour and percentage of well product of gelled UO 3 were noticed. The density and O/U ratio of end product (UO 2 kernel) was determined, the percentage of well product of all steps process was also determined. The three factor were used to chose the optimum concentration of uranyl nitrate solution. From this investigation it was concluded that the optimum concentration of uranyl nitrate was 600 g/l uranium with free nitric acid 0,9 - 1,0 N, the percentage of well product was 97% density of 6.12 - 4.8 g/cc and O/U ratio of 2.15 - 2.06. (author)

Mechanism of the reduction of hexavalent chromium by organo-montmorillonite supported iron nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Wu, Pingxiao, E-mail: pppxwu@scut.edu.cn [College of Environmental Science and Engineering, South China University of Technology, Guangzhou 510006 (China); Li, Shuzhen [School of Chemical and Environmental Engineering, Wuyi University, Jiangmen, Guangdong Province 529020 (China); Ju, Liting [College of Environmental Science and Engineering, South China University of Technology, Guangzhou 510006 (China); Zhu, Nengwu [College of Environmental Science and Engineering, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, Guangzhou 510006 (China); The Key Laboratory of Environmental Protection and Eco-Remediation of Guangdong Regular Higher Education Institutions (China); Wu, Jinhua; Li, Ping [College of Environmental Science and Engineering, South China University of Technology, Guangzhou 510006 (China); Dang, Zhi [College of Environmental Science and Engineering, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, Guangzhou 510006 (China); The Key Laboratory of Environmental Protection and Eco-Remediation of Guangdong Regular Higher Education Institutions (China)

2012-06-15

Highlights: Black-Right-Pointing-Pointer Organo-montmorillonite supported iron nanoparticles were found to be more efficient in the removal of Cr(VI) than unsupported iron nanoparticles. Black-Right-Pointing-Pointer The iron nanoparticles were accommodated by the sectional structure of the clay minerals which were helpful to protect the nanoparticles from aggregating. Black-Right-Pointing-Pointer XPS and XANES provided some direct information about the reduction mechanisms. Black-Right-Pointing-Pointer The structure of the supported iron nanoparticles was stable in the reaction with Cr(VI). - Abstract: Iron nanoparticles exhibit greater reactivity than micro-sized Fe{sup 0}, and they impart advantages for groundwater remediation. In this paper, supported iron nanoparticles were synthesized to further enhance the speed and efficiency of remediation. Natural montmorillonite and organo-montmorillonite were chosen as supporting materials. The capacity of supported iron nanoparticles was evaluated, compared to unsupported iron nanoparticles, for the reduction of aqueous Cr(VI). The reduction of Cr(VI) was much greater with organo-montmorillonite supported iron nanoparticles and fitted the pseudo-second order equation better. With a dose at 0.47 g/L, a total removal capacity of 106 mg Cr/g Fe{sup 0} was obtained. Other factors that affect the efficiency of Cr(VI) removal, such as pH values, the initial Cr(VI) concentration and storage time of nanoparticles were investigated. X-ray photoelectron spectrometry (XPS) and X-ray absorption near edge structure (XANES) were used to figure out the mechanism of the removal of Cr(VI). XPS indicated that the Cr(VI) bound to the particle surface was completely reduced to Cr(III) under a range of conditions. XANES confirmed that the Cr(VI) reacted with iron nanoparticles was completely reduced to Cr(III).

Solvent extraction of uranyl nitrate (1962); Extraction du nitrate d'uranyle par solvant (1962)

Energy Technology Data Exchange (ETDEWEB)

Talmont, X; Regnaut, P [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires; Durandet, J; Renault, Ph; Gladel, Y L [Institut Francais du Petrole (IFP), Dept. de Physico-Chimie Appliquee, 92 - Rueil-Malmaison (France)

1962-07-01

The transfer of uranyl nitrate from an aqueous acid phase into a solvent (dilute tributylphosphate) is attended by nitric acid transfer. In these conditions, equilibrium data cannot be represented by a plane curve, which complicates the determination of the efficiency of the extractor used, i.e. the calculation of either the number of theoretical plates or the number of transfer units equivalent to the apparatus. The authors are presenting a simple method for estimating the efficiency of a column, based upon either uranium or acid transfer. This method can be used when the profile of uranium and acid concentrations in a phase circulating in the equipment bas been previously determined. On another hand, it enables to study the variation of local efficiency, i.e. the efficiency of different sections of the column. (authors) [French] Le transfert du nitrate d'uranyle d'une phase aqueuse acide dans un solvant (phosphate de tributyle dilue) s'accompagne d'un transfert d'acide nitrique. Dans ces conditions, les donnees d'equilibre ne sont pas representees par une courbe plane, ce qui complique la determination de l'efficacite de l'extracteur utilise, c'est-a-dire le calcul, soit du nombre d'etages theoriques, soit du nombre d'unites de transfert auquel l'appareil est equivalent. Les auteurs presentent une methode simple d'evaluation de l'efficacite d'une colonne basee, soit sur le transfert d'uranium, soit sur celui d'acide. Cette methode est utilisable lorsqu'en a determine au prealable le profil des concentrations en uranium et en acide d'une phase circulant dans l'appareil. Elle permet, d'autre part, d'etudier la variation de l'efficacite locale, c'est-a-dire l'efficacite de differentes sections de la colonne. (auteurs)

Uranyl citrate dimers as guests in a copper-bipyridine framework: a novel hetero-metallic inorganic-organic hybrid compound

International Nuclear Information System (INIS)

Thuery, P.

2007-01-01

Reaction of uranyl nitrate with citric acid (H 4 cit) in the presence of copper(II) bis(tri-fluoro-methane-sulfonate) and 4,4'-bipyridine (bipy) under hydrothermal conditions gave the mixed complex[Cu(bipy) 2 (H 2 O) 2 ][UO 2 (Hcit)(H 2 O)] 2 .5H 2 O, in which di-anionic uranyl citrate dimers are incorporated in the interlayer spaces of the [Cu(bipy) 2 (H 2 O) 2 ] n 2n+ square grid assemblage. An extended hydrogen bonding network links the uranyl complex units together and also to the grid framework, resulting in the formation of a 3-D assemblage held by weak interactions. (author)

Formation of the second organic phase during uranyl nitrate extraction from aqueous solution by 30% tributylphosphate solution in paraffin

International Nuclear Information System (INIS)

Yhrkin, V.G.

1996-01-01

For extraction systems aqueous solution of uranyl nitrate-30% solution of tributylphosphate in individual paraffins from C 13 to C 17 the influence of the second organic phase of uranyl nitrate concentration in aqueous and organic phases, the length of hydrocarbon chain of paraffin hydrocarbon and temperature from 25 to 50 deg C on formation conditions has been defected. A special method of achieving the conditions of organic phase stratification from three-phase region, involving definition of equilibrium phases composition by density and refractive index, has been elaborated for more precise definition of organic phase homogeneity region. It has been revealed that without addition of nitric acid to uranyl nitrate solution the organic phase homogeneity limits can be achieved solely on paraffins C 15 , C 16 and C 17 and only under conditions similar to equeous phase saturation in terms of uranyl nitrate. 16 refs., 2 figs

Hydrothermal synthesis of uranyl squarates and squarate-oxalates: hydrolysis trends and in situ oxalate formation.

Science.gov (United States)

Rowland, Clare E; Cahill, Christopher L

2010-07-19

We report the synthesis of two uranyl squarates and two mixed-ligand uranyl squarate-oxalates from aqueous solutions under hydrothermal conditions. These products exhibit a range of uranyl building units from squarates with monomers in (UO(2))(2)(C(4)O(4))(5).6NH(4).4H(2)O (1; a = 16.731(17) A, b = 7.280(8) A, c = 15.872(16) A, beta = 113.294(16) degrees , monoclinic, P2(1)/c) and chains in (UO(2))(2)(OH)(2)(H(2)O)(2)(C(4)O(4)) (2; a = 12.909(5) A, b = 8.400(3) A, c = 10.322(4) A, beta = 100.056(7) degrees , monoclinic, C2/c) to two squarate-oxalate polymorphs with dimers in (UO(2))(2)(OH)(C(4)O(4))(C(2)O(4)).NH(4).H(2)O (3; a = 9.0601(7) A, b = 15.7299(12) A, c = 10.5108(8) A, beta = 106.394(1) degrees , monoclinic, P2(1)/n; and 4; a = 8.4469(6) A, b = 7.7589(5) A, c = 10.5257(7) A, beta = 105.696(1) degrees , monoclinic, P2(1)/m). The dominance at low pH of monomeric species and the increasing occurrence of oligomeric species with increasing pH suggests that uranyl hydrolysis, mUO(2)(2+) + nH(2)O right harpoon over left harpoon [(UO(2))(m)(OH)(n)](2m-n) + nH(+), has a significant role in the identity of the inorganic building unit. Additional factors that influence product assembly include in situ hydrolysis of squaric acid to oxalic acid, dynamic metal to ligand concentration, and additional binding modes resulting from the introduction of oxalate anions. These points and the effects of uranyl hydrolysis with changing pH are discussed in the context of the compounds presented herein.

Recovery of uranium from uranyl nitrate raffinate. Contributed Paper PE-06

International Nuclear Information System (INIS)

Anilkumar Reddy, A.M.; Shiva Kumar, M.; Varadan, K.M.K.; Babaji, P.; Sairam, S. Sheela; Saibaba, N.

2014-01-01

At New Uranium Oxide Fuel Plant, NUOFP(O) of Nuclear Fuel Complex (NFC), the Uranyl Nitrate Raffinate (UNR) generated during solvent extraction process is washed with Treated Lean Solvent(TLS) to recover residual U. Earlier this UNR consisting of 0.5-1 gm/l and 2.5 FA was neutralised with vapour ammonia. The slurry was then filtered over pre coat drum filter and the resultant Uranyl Nitrate Raffinate cake (UNRC) was stored in polyethylene lined MS drums. The valuable U was thus being locked up in UNRC. Also, the storage of UNRC drums required lot of floor space which have to be repacked frequently to contain the radioactivity. Hence the need has come to avoid the generation of UNRC and the recovery of U from the already generated UNRC. The generation of UNRC was avoided by developing alternate process of UNR treatment with Treated Lean Solvent for the removal of residual U and the resulting Acidic Raffinate Slurry (ARS) is disposed. The Uranium recovery from UNRC is done by dissolving the cake in Uranyl Nitrate Raffinate solution to leach the hexavalent Uranium by utilizing the free acidity in UNR. The leaching time is about six hours and the uranium forms uranyl nitrate. The resulting leach solutions are relatively dilute but complex acidic nitrate solutions containing wide variety of ions. Metallic ions commonly present include uranium, iron, magnesium, aluminium, sodium, calcium etc. The uranium concentration is normally 1-1.5 g/L. This uranium is separated by solvent extraction. The active agent in solvent extraction is Tri Butyl Phosphate in kerosene that can selectively extract uranium into an organic complex which is insoluble in aqueous. The organic used for extraction is Treated Lean Solvent in the quality of freshly prepared solvent and the resulting Acidic Raffinate Slurry is disposed by sale. The leaching of Uranium from UNRC was done in plant scale and about 1200 kgs of UNRC was successfully processed in trial batch. The paper deals with details of

Extraction of rare earth metals (3) from aqueous solutions containing thorium and uranyl nitrates

International Nuclear Information System (INIS)

Pyartman, A.K.; Kopyrin, A.A.; Berinskij, A.E.; Keskinov, V.A.

2000-01-01

Isotherms of extraction of rare earth metals (3) from aqueous solutions containing thorium and uranyl nitrates by solutions of tributylphosphate (TBP) and diisooctylmethylphosphonate (DIOMP) in kerosene at 298.15 Deg C and pH 1 are presented. Equations for description of interphase distribution of components of the systems considered are suggested. These equations describe distribution of components adequately in the systems of thorium nitrate (uranyl nitrate) - rare earth nitrates - (TBP, DIOMP) in the case of wide variation of phase compositions. Dependences of separation factors on composition of aqueous phase are considered [ru

Preparation of CIGS thin films by HiPIMS or DC sputtering and various selenization processes

Czech Academy of Sciences Publication Activity Database

Olejníček, Jiří; Hubička, Zdeněk; Kšírová, Petra; Kment, Štěpán; Brunclíková, Michaela; Kohout, Michal; Čada, Martin; Darveau, S.A.; Exstrom, C.L.

2013-01-01

Roč. 16, č. 2 (2013), s. 314-319 ISSN 1203-8407 R&D Projects: GA MŠk LH12045 Institutional support: RVO:68378271 Keywords : CIGS * HIPIMS * selenization * nanocrystals * solar energy * sputtering * thin films Subject RIV: BL - Plasma and Gas Discharge Physics Impact factor: 1.106, year: 2013 http://www.ingentaconnect.com/content/stn/jaots/2013/00000016/00000002/art00015

Studies on structural, optical, and photoelectric properties of CdS{sub 1-x}Se{sub x} films fabricated by selenization of chemical bath deposited CdS films

Energy Technology Data Exchange (ETDEWEB)

Lu, Tianyu; Gu, Han; Ge, Zhenhua; Zhang, Lei; Wang, Zhicheng; Fang, Yong; Han, Zhida; Qian, Bin; Jiang, Xuefan [Department of Physics, Changshu Institute of Technology, Changshu (China); Wu, Wangping [School of Mechanical Engineering, Changzhou University, Changzhou (China)

2017-02-15

In this paper, high-photosensitive CdS{sub 1-x}Se{sub x} films are synthesized by a two-step technique, which includes the chemical bath deposition of CdS films and a following selenization process. The structural, optical, and photoelectric properties of the CdS{sub 1-x}Se{sub x} films were investigated. With the substitution of selenium for sulfur atoms, grain sizes of the as-prepared CdS{sub 1-x}Se{sub x} films are effectively enlarged and reach the scales of the films thickness when the selenization temperature exceeds 450 C. With increasing the selenization temperature from 350 to 550 C, the band gaps of CdS{sub 1-x}Se{sub x} films gradually decrease from 2.37 to 1.82 eV. Under the co-action of the grain-size enlargement and band-gap decrease, the CdS{sub 1-x}Se{sub x} films fabricated at 450 C show very pronounced photosensitivity. Noteworthy, the ratio of photo to dark conductivity of the CdS{sub 1-x}Se{sub x} film selenized at 450 C reaches 1.1 x 10{sup 5}, suggesting a promising application potential in the photoelectric devices. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Critical experiments on low enriched uranyl nitrate solution with STACY

International Nuclear Information System (INIS)

Miyoshi, Yoshinori

1996-01-01

As the STACY started steady operations, systematic criticality data on low enriched uranyl nitrate solution system could be accumulated. Main experimental parameters for the cylindrical tank of 60 cm in diameter were uranium concentration and the reflector condition. Basic data on a simple geometry will be helpful for the validation of the standard criticality safety codes, and for evaluating the safety margin included in the criticality designs. Experiments on the reactivity effects of structural materials such as borated concrete and polyethylene are on schedule next year as the second series of experiments using 10 wt% enriched uranyl solution. Furthermore, neutron interacting experiments with two slab tanks will be performed to investigate the fundamental properties of neutron interaction effects between core tanks. These data will be useful for making more reasonable calculation models and for evaluating the safety margin in the criticality designs for the multiple unit system. (J.P.N.)

Criticality parameters for uranyl nitrate or plutonium nitrate systems in tributyl phosphate/kerosine and water

International Nuclear Information System (INIS)

Weber, W.

1985-01-01

This report presents the calculated values of smallest critical masses and volumina and neutron physical parameters for uranyl nitrate (3, 4, 5% U-235) or plutonium nitrate (5% Pu-240), each in a 30 per cent solution of tributyl phosphate (TBP)/kerosine. For the corresponding nitrate-water solutions, newly calculated results are presented together with a revised solution density model. A comparison of the data shows to what extent the criticality of nitrate-TBP/kerosine systems can be assessed on the basis of nitrate-water parameters, revealing that such data can be applied to uranyl nitrate/water systems, taking into account that the smallest critical mass of uranyl nitrate-TBP/kerosine systems, up to a 5 p.c. U-235 enrichment, is by 4.5 p.c. at the most smaller than that of UNH-water solutions. Plutonium nitrate (5% Pu-240) in the TBP/kerosine solution will have a smallest critical mass of up to 7 p.c. smaller, as compared with the water data. The suitability of the computing methods and cross-sections used is verified by recalculating experiments carried out to determine the lowest critical enrichment of uranyl nitrate. The calculated results are well in agreement with experimental data. The lowest critical enrichment is calculated to be 2.10 p.c. in the isotope U-235. (orig.) [de

Series of mixed uranyl-lanthanide (Ce, Nd) organic coordination polymers with aromatic polycarboxylates linkers.

Science.gov (United States)

Mihalcea, Ionut; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry

2012-09-17

Three series of mixed uranyl-lanthanide (Ce or Nd) carboxylate coordination polymers have been successfully synthesized by means of a hydrothermal route using either conventional or microwave heating methods. These compounds have been prepared from mixtures of uranyl nitrate, lanthanide nitrate together with phthalic acid (1,2), pyromellitic acid (3,4), or mellitic acid (5,6) in aqueous solution. The X-ray diffraction (XRD) single-crystal revealed that the phthalate complex (UO(2))(4)O(2)Ln(H(2)O)(7)(1,2-bdc)(4)·NH(4)·xH(2)O (Ln = Ce(1), Nd(2); x = 1 for 1, x = 0 for 2), is based on the connection of tetranuclear uranyl-centered building blocks linked to discrete monomeric units LnO(2)(H(2)O)(7) via the organic species to generate infinite chains, intercalated by free ammonium cations. The pyromellitate phase (UO(2))(3)Ln(2)(H(2)O)(12)(btec)(3)·5H(2)O (Ce(3), Nd(4)) contains layers of monomeric uranyl-centered hexagonal and pentagonal bipyramids linked via the carboxylate arms of the organic molecules. The three-dimensionality of the structure is ensured by the connection of remaining free carboxylate groups with isolated monomeric units LnO(2)(H(2)O)(7). The network of the third series (UO(2))(2)(OH)Ln(H(2)O)(7)(mel)·5H(2)O (Ce(5), Nd(6)) is built up from dinuclear uranyl units forming layers through connection with the mellitate ligands, which are further linked to each other through discrete monomers LnO(3)(H(2)O)(6). The thermal decomposition of the various coordination complexes led to the formation of mixed uranium-lanthanide oxide, with the fluorite-type structure at 1500 °C (for 1, 2) or 1400 °C for 3-6. Expected U/Ln ratio from the crystal structures were observed for compounds 1-6.

Study of the extraction mechanisms by TBP saturated by uranyl nitrate; Etude des mecanismes d'extraction du TBP sature par le nitrate d'uranyle

Energy Technology Data Exchange (ETDEWEB)

Meze, F

2004-02-15

This work deals with a particular phenomenon likely to occur in the nuclear waste reprocessing process PUREX. It was shown earlier by Russian works that the extractant molecule, tributyl phosphate (TBP), saturated by uranyl nitrate keeps its extraction capacities for nitric acid and tetravalent actinides. This study is composed of three parts. Firstly, some liquid-liquid extraction experiments were conducted to verify the ability of TBP saturated by uranyl nitrate to conserve its extraction capacities for nitric acid. Then, during these experiments, the UV and infrared spectra of both phases were recorded to obtain the organic phase speciation. At last, the informations gathered during the experimental part were used to build a general species distribution model of the H{sub 2}O/HNO{sub 3}/UO{sub 2}(NO{sub 3}){sub 2}/TBP system. (author)

Thermal decomposition kinetics of ammonium uranyl carbonate

International Nuclear Information System (INIS)

Kim, E.H.; Park, J.J.; Park, J.H.; Chang, I.S.; Choi, C.S.; Kim, S.D.

1994-01-01

The thermal decomposition kinetics of AUC [ammonium uranyl carbonate; (NH 4 ) 4 UO 2 (CO 3 ) 3 [ in an isothermal thermogravimetric (TG) reactor under N 2 atmosphere has been determined. The kinetic data can be represented by the two-dimensional nucleation and growth model. The reaction rate increases and activation energy decreases with increasing particle size and precipitation time which appears in the particle size larger than 30 μm in the mechano-chemical phenomena. (orig.)

Derivation of an empirical formula for determining water content of mixed uranyl nitrate-thorium nitrate solutions

International Nuclear Information System (INIS)

Min, Duck Kee; Choi, Byung Il; Ro, Seung Gy; Eom, Tae Yoon; Kim, Zong Goo

1986-01-01

Densities of a large number of mixed uranyl nitrate-thorium nitrate solutions were measured with pycnometer. By the least squares analysis of the experimental result, an empirical formula for determining water content of mixed uranyl nitrate-thorium nitrate solutions as functions of uranium concentration, thorium concentration and nitric acid normality is derived; W=1.0-0.3580 C u -0.4538 C Th -0.0307H + where W, C u , C Th , and H + stand for water content(g/cc), uranium concentration (g/cc), thorium concentration(g/cc), and nitric acid normality, respectively. Water contents of the mixed uranyl nitrate-thorium nitrate solutions are calculated by using the empirical formular, and compared with the values calculated by Bouly's equation in which an additional data, solution density, is required. The two results show good agreements within 2.7%. (Author)

Investigation of regularities of uranyl salts complexing with neutral bases in nonaqueous media

International Nuclear Information System (INIS)

Kobets, L.V.; Buchikhin, E.P.

1986-01-01

Anhydrous uranyl chloride complexing with neutral oxygen-containing organic bases (sulfoxides, organic phosphates, phosphinates, phosphinoxides, N-oxides) in the acetone medium depending on the donor capacity of neutral molecules is discussed. The constants of 1:1 complexes dissociation are shown to detect no correlation with the donor capacity of neutral bases. At the same time stability constants of complexes increase as the donor capacity of ligands grows. But the dependence is of a complex character and is determined by the nature of neutral molecules. Estimation of uranyl chloride and 0-donor contributions into the values of stability constants and complex formation heats is given

Controlled deprotection and reorganization of uranyl oxo groups in a binuclear macrocyclic environment

Energy Technology Data Exchange (ETDEWEB)

Jones, Guy M.; Arnold, Polly L.; Love, Jason B. [EaStCHEM School of Chemistry, University of Edinburgh (United Kingdom)

2012-12-07

Switching on uranium(V) reactivity: The silylated uranium(V) dioxo complex [(Me{sub 3}SiOUO){sub 2}(L){sub 2}] (A) is inert to oxidation, but after two-electron reduction to [(Me{sub 3}SiOUO){sub 2}(L)]{sup 2-} (1), it can be desilylated to form [OU(μ-O){sub 2}UO(L){sub 2}]{sup 2-} (2) with reinstated uranyl character. Removal of the silyl group uncovers new redox and oxo rearrangement chemistry for uranium, thus reforming the uranyl motif and involving the U{sup VI/V} couple in dioxygen reduction. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Determination of parameters dissolution of yellow-cake. Production of uranyl nitrate - Gas precipitation of AUC

International Nuclear Information System (INIS)

Mellah, A.

1987-07-01

The different stages of the purification cycle of yellow-cakes have been studied thoroughly in order to obtain an ammonium uranyl carbonate (AUC) as an intermediate product of uranium dioxide (UO 2 ). The optimal parameters of yellow-cake dissolution, filtration, extraction by solvent, scrubbing and stripping were determined. An original program of thermodynamic calculation was developed for the determination of the free energies of yellow-cake dissolution reactions. Different numerical methods were used to determine the kinetic constant, the reaction order and correlation equations of uranyl nitrate density as a function of U and H + concentrations, before and after the extraction cycle. For the first time, Algerian filteraids were used for the filtration of uranyl nitrate solutions with satisfactory results. A laboratory designed installation enabled the precipitation of AUC by injection of ammonia and carbon dioxide gases. Interesting results have been obtained and further investigations should be carried out in order to optimize all the paremeters of the gas precipitation of AUC

Novel organo soluble poly imides and polyimide nano composites based on 1,4-bis(4-aminophenyl)-1,3,4-oxadiaz olyl)benzene, BAOB, via BAOB-modified organo clay

International Nuclear Information System (INIS)

Mansoori, Y.; Darvishi, K.

2014-01-01

New, thermally stable poly imides (PI) containing a 1,3,4-oxadiazole ring in the polymer backbone based on 1,4-bis((4-aminophenyl)-1,3,4-oxadiaz olyl)benzene, BAOB, were synthesized. The prepared polymers were soluble in polar and aprotic solvents. The obtained results reveal that within the prepared polymers, polyimide which has been obtained from BAOB and 4,4-oxy diphthalic dianhydride, ODPA, has the most improved thermal properties. In the next part, thermally stable organophilic clay was obtained via cation exchange reaction between sodium montmorillonite (Na-MMT) and the hydrochloride salt of BAOB. Then, a series of PI/clay nano composite materials (PCNs) were synthesized from the in situ polymerization reaction of BAOB and ODPA via thermal imidization, BAOB-MMT was used as the filler at different concentrations. Intercalation of polymer chains within the organo clay galleries was confirmed by W XRD. The glass transition temperature is increased with respect to pristine PI for PCNs 1-3 wt %. At high clay loadings, the aggregation of organo clay particles results in a decrease in T g . In the Sem images of the pure polymer too many micro-cracks were observed in the background, while surface homogeneity of PCN 1 wt % is increased and micro-cracks are reduced. (Author)

Novel organo soluble poly imides and polyimide nano composites based on 1,4-bis(4-aminophenyl)-1,3,4-oxadiaz olyl)benzene, BAOB, via BAOB-modified organo clay

Energy Technology Data Exchange (ETDEWEB)

Mansoori, Y.; Darvishi, K., E-mail: ya_mansoori@yahoo.com [University of Mohaghegh Ardabili, Faculty of Science, Department of Applied Chemistry, Daneshgah, Ardabil (Iran, Islamic Republic of)

2014-10-01

New, thermally stable poly imides (PI) containing a 1,3,4-oxadiazole ring in the polymer backbone based on 1,4-bis((4-aminophenyl)-1,3,4-oxadiaz olyl)benzene, BAOB, were synthesized. The prepared polymers were soluble in polar and aprotic solvents. The obtained results reveal that within the prepared polymers, polyimide which has been obtained from BAOB and 4,4-oxy diphthalic dianhydride, ODPA, has the most improved thermal properties. In the next part, thermally stable organophilic clay was obtained via cation exchange reaction between sodium montmorillonite (Na-MMT) and the hydrochloride salt of BAOB. Then, a series of PI/clay nano composite materials (PCNs) were synthesized from the in situ polymerization reaction of BAOB and ODPA via thermal imidization, BAOB-MMT was used as the filler at different concentrations. Intercalation of polymer chains within the organo clay galleries was confirmed by W XRD. The glass transition temperature is increased with respect to pristine PI for PCNs 1-3 wt %. At high clay loadings, the aggregation of organo clay particles results in a decrease in T{sub g}. In the Sem images of the pure polymer too many micro-cracks were observed in the background, while surface homogeneity of PCN 1 wt % is increased and micro-cracks are reduced. (Author)

A microscopic study of the action of uranyl acetate on the erythrocyte at varying molarity and toxicity

International Nuclear Information System (INIS)

Wyatt, J.H.

1977-03-01

Phase contrast and dark field microphotographs were made to record variation of the shape and size changes seen when human erythrocytes are exposed in a number of ways to uranyl acetate in vitro. The degree of hemolysis produced by varying the toxicity of the uranyl acetate solutions was measured, and the results are discussed with particular reference to the possible influence of pH. (author)

Selectivity in Ligand Binding to Uranyl Compounds: A Synthetic, Structural, Thermodynamic and Computational Study

Energy Technology Data Exchange (ETDEWEB)

Arnold, John [Univ. of California, Berkeley, CA (United States)

2017-12-06

The uranyl cation (UO₂²⁺) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. We believe that the goal of developing a practical system for uranium separation from seawater will not be attained without new insights into our existing fundamental knowledge of actinide chemistry. We posit that detailed studies of the kinetic and thermodynamic factors that influence interactions between f-elements and ligands with a range of donor atoms is essential to any major advance in this important area. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. We anticipate that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials.

Renal hemodynamics in uranyl acetate-induced acute renal failure of rabbits

International Nuclear Information System (INIS)

Sudo, M.; Honda, N.; Hishida, A.; Nagase, M.

1977-01-01

The role of renal hemodynamic alterations in the curtailment of renal function was studied in rabbits with uranyl acetate-induced acute renal failure. The day following the i.v. injection of uranyl acetate (2 mg/kg of body wt), renal blood flow (RBF) and clearance of creatinine (Ccr) decreased to approximately 60 and 20% of controls, respectively. Intracortical fractional flow distribution, estimated by radioactive microsphere method, did not change. The extraction ratio of para-aminohippurate (EPAH) decreased and the renal extraction of sodium (CNa/Ccr) increased, with minimal structural change in the kidney. Urine output increased two to three times that of the control. After three days oliguria appeared despite complete recovery of RBF. The zonal flow redistributed toward the deep cortex. CCr and EPAH reached their minimums, concomitantly with tubular necrosis and intratubular casts. After seven days animals could be divided into the oliguric and diuretic groups. CCr and EPAH were higher in the diuretic group, while there was no significant difference in RBF and the flow distribution between groups. Regeneration of damaged tubular cells was found in the diuretic group but not in the oliguric group. The findings suggest the minor roles of RBF and the intracortical flow distribution, and a fundamental role of back leakage of filtrate across damaged tubular epithelium in the maintenance of reduced CCR and urine output during the oliguric stage in rabbits with uranyl acetate-induced renal failure

Process for obtaining ammonium uranyl tri carbonate

International Nuclear Information System (INIS)

Santos, L.R. dos; Riella, H.G.

1992-01-01

The procedure adopted for obtaining Ammonium Uranyl Carbonate (AUC) from uranium hexafluoride (U F 6 ) in a aqueous solutions of ammonium hydrogen carbonate is described in this work. The precipitation is made in temperature and pH controlled. This process consists of three steps: evaporation of U F 6 , AUC precipitation and filtration of the AUC slurry. An attempt is made of correlate the parameters involved in the precipitation process of AUC with its and U O 2 characteristics. (author)

La aplicación de abono organo-mineral: una alternativa para la producción de maíz (Zea mays L., en suelos pardos con carbonatos.

Directory of Open Access Journals (Sweden)

Ignacio Corrales Garriga

2013-04-01

Full Text Available RESUMEN Durante tres años se condujo un experimento en áreas del Instituto de Investigaciones de Viandas Tropicales (INIVIT de Camagüey, empleando diferentes abonos organo-mineral, con el objetivo de conocer su influencia en el rendimiento del maíz (Zea maiz, L, sobre un suelo Pardo Sialítico Mullido Carbonatado de pH ligeramente ácido, bajo contenido de P2O5 y medio de K2O y materia orgánica. Para las mezclas organo-mineral se emplearon como abonos orgánicos el estiércol vacuno y la cachaza y como fertilizantes minerales, el superfosfato triple y el cloruro de potasio. El organo-mineral se aplicó en el momento de la siembra a una dosis de 745 kg ha1 de acuerdo a cada tratamiento, los que fueron replicados 4 veces en un diseño de bloques al azar. Se midió el rendimiento y sus componentes y se tomaron muestras de suelo para conocer la variación de sus propiedades. Los datos fueron evaluados por un análisis de varianza de clasificación doble y se aplicó la prueba de rango múltiple de Duncan para un nivel de significación del 5 %. Los resultados muestran que el empleo de los abonos organo-minerales favorece el rendimiento, reducen los fertilizantes químicos a emplear y mejoran las propiedades del suelo. ORGANO-MINERAL FERTILIZER APPLICATION: AN ALTERNATIVE FOR PRODUCTION OF CORN (Zea mays L., IN SIALYTIC BROWN CARBONATED SOIL. ABSTRACT. For three years, an experiment was conducted in areas of the Research Institute (INIVIT Camaguey , using different organo- mineral fertilizers , in order to study its influence on the performance of maize ( Zea mays , L on a Fluffy Sialytic Brown Carbonated soil slightly acidic pH , low P2O5 and K2O and medium organic matter. For organo- mineral mixtures were used as organic fertilizers and cow manure and cachaza and mineral fertilizer, triple superphosphate and potassium chloride. The organo- mineral was applied at the time of planting at a dose of 745 kg ha1 according to each treatment, which

Quenching of excited uranyl ion during its photochemical reduction with triphenyl-phosphine : Part IV - effect of heterocyclic molecules

International Nuclear Information System (INIS)

Sidhu, M.S.; Bhatia, P.V.K.

1994-01-01

The presence of heterocyclic compounds triggers off a competition between photophysical and photochemical annihilation of excited uranyl ion during its photochemical reduction with triphenylphosphine. This competition is used to measure Stern-Volmer constant using UV visible spectrophotometer for quenching the uranyl ion luminescence with a number of heterocyclic molecules viz., pyridine, thiophene bipyridyl, tetrahydrofuran and piperidine. (author). 7 refs., 2 figs., 1 tab

Organo-gel de heptano: diagrama de fases e aplicações sintéticas

Directory of Open Access Journals (Sweden)

Queiroz Neide

1999-01-01

Full Text Available The phase diagram formation of microemulsion-based gels composed of an anionic surfactant aerosol-OT sodium bis (2-ethylhexyl-sulphosuccinate, water, gelatin and an organic solvent is presented for heptane. The stability of this organo- gel, when an enzyme is immobilized is discussed in terms of its reutilization in various esters synthesis.

Ultrastructure changes produced by the action of uranyl acetate on the human erythrocyte in vitro

Energy Technology Data Exchange (ETDEWEB)

Wyatt, J H

1975-06-01

Human erythrocytes exposed in vitro to low concentrations of uranyl ions are immediately changed in shape to stomatocytes. Electron microscope examination demonstrates that cellular damage is confined to the plasma membrane. Endocytosis of the cell membrane produces groups of inside out membrane-lined vesicles within the cell; lipid from the membrane enters the cell, giving rise to intracellular myelin figures, and breaks are seen in the cell membrane. It is proposed that the lipid fraction of the cell membrane is the primary target for damage by uranyl ions.

Ultrastructure changes produced by the action of uranyl acetate on the human erythrocyte in vitro

International Nuclear Information System (INIS)

Wyatt, J.H.

1975-06-01

Human erythrocytes exposed in vitro to low concentrations of uranyl ions are immediately changed in shape to stomatocytes. Electron microscope examination demonstrates that cellular damage is confined to the plasma membrane. Endocytosis of the cell membrane produces groups of inside out membrane-lined vesicles within the cell; lipid from the membrane enters the cell, giving rise to intracellular myelin figures, and breaks are seen in the cell membrane. It is proposed that the lipid fraction of the cell membrane is the primary target for damage by uranyl ions. (author)

Bases for DOT exemption uranyl nitrate solution shipments

International Nuclear Information System (INIS)

Moyer, R.A.

1982-07-01

Uranyl nitrate solutions from a Savannah River Plant reprocessing facility have been transported in cargo tank trailers for more than 20 years without incident during transit. The solution is shipped to Oak Ridge for further processing and returned to SRP in a solid metal form for recycle. This solution, called uranyl nitrate hexahydrate (UNH) solution in Department of Transportation (DOT) regulations, is currently diluted about 2-fold to comply with DOT concentration limits (10% of low specific activity levels) specified for bulk low specific activity (LSA) liquid shipments. Dilution of the process solution increases the number of shipments, the cost of transportation, the cost of shipper preparations, the cost of further reprocessing in the receiving facility to first evaporate the added water, and the total risk to the population along the route of travel. However, the radiological risk remains about the same. Therefore, obtaining an exemption from DOT regulations to permit shipment of undiluted UNH solution, which is normally about two times the present limit, is prudent and more economical. The radiological and nonradiological risks from shipping a unit load of undiluted solution are summarized for the probable route. Data and calculations are presented on a per load or per shipment basis throughout this memorandum to keep it unclassified

Effect of Solvent-Assisted Nanoscaled Organo-Gels on Morphology and Performance of Organic Solar Cells

DEFF Research Database (Denmark)

Zuo, Li-Jian; Hu, Xiao-Lian; Ye, Tao

2012-01-01

with that of the organo-gels in solution. Through this knowledge, we eventually achieve controlled morphology and optimized organic solar cells (OSCs) performance. Our results present a significant step forward for understanding the self-assembly behavior of conjugated polymers, control of their morphology...... and optimization of OSC performance....

Algorithmic crystal chemistry: A cellular automata approach

International Nuclear Information System (INIS)

Krivovichev, S. V.

2012-01-01

Atomic-molecular mechanisms of crystal growth can be modeled based on crystallochemical information using cellular automata (a particular case of finite deterministic automata). In particular, the formation of heteropolyhedral layered complexes in uranyl selenates can be modeled applying a one-dimensional three-colored cellular automaton. The use of the theory of calculations (in particular, the theory of automata) in crystallography allows one to interpret crystal growth as a computational process (the realization of an algorithm or program with a finite number of steps).

Ratiometric colorimetric determination of coenzyme A using gold nanoparticles and a binuclear uranyl complex as optical probes

International Nuclear Information System (INIS)

Wu, Rurong; Liao, Lifu; Li, Shijun; Yang, Yanyan; Xiao, Xilin; Nie, Changming

2016-01-01

We describe a ratiometric colorimetric method for the determination of coenzyme A (CoA) by using gold nanoparticles (AuNPs) and bis-uranyl-bis-sulfosalophen (BUBSS) as optical probes. BUBSS is a binuclear uranyl complex and formed through the chelating reaction of two uranyl ions with bis-sulfosalophen. CoA is captured by the AuNPs via the thiol group and this leads to the formation of CoA-AuNPs. In a second step, BUBSS binds two CoA-AuNPs through a coordination reaction between the uranyl ions in BUBSS and the phosphate groups in CoA-AuNPs. This causes the CoA-AuNPs to aggregate and results in a color change from wine red to blue. A ratiometric colorimetric assay was established for CoA based on the ratiometric measurement of absorbance changes at 650 and 525 nm. Their ratio is linearly related to the concentration of CoA in the 0 to 1.2 μmol⋅L -1 range, with a 6 nmol⋅ L- 1 detection limit under optimal conditions. The method was successfully applied to the determination of CoA in spiked liver samples with recoveries between 99.4 and 102.6 %. (author)

Sodium dodecyl sulfate coated alumina modified with a new Schiff's base as a uranyl ion selective adsorbent

Energy Technology Data Exchange (ETDEWEB)

Tashkhourian, J., E-mail: tashkhourian@susc.ac.ir [Department of Chemistry, College of Science, Shiraz University, 71454 Shiraz (Iran, Islamic Republic of); Moradi Abdoluosofi, L.; Pakniat, M. [Department of Chemistry, Faculty of Science, Persian Gulf University, Bushehr 75169 (Iran, Islamic Republic of); Montazerozohori, M. [Department of Chemistry, Faculty of Science, Yasouj University, Yasouj (Iran, Islamic Republic of)

2011-03-15

A simple and selective method was used for the preconcentration and determination of uranium(VI) by solid-phase extraction (SPE). In this method, a column of alumina modified with sodium dodecyl sulfate (SDS) and a new Schiff's base ligand was prepared for the preconcentration of trace uranyl(VI) from water samples. The uranium(VI) was completely eluted with HCl 2 M and determined by a spectrophotometeric method with Arsenazo(III). The preconcentration steps were studied with regard to experimental parameters such as amount of extractant, type, volume and concentration of eluent, pH, flow rate of sample source and tolerance limit of diverse ions on the recovery of uranyl ion. A preconcentration factor more than 200 was achieved and the average recovery of uranyl(VI) was 99.5%. The relative standard deviation was 1.1% for 10 replicate determinations of uranyl(VI) ion in a solution with a concentration of 5 {mu}g mL{sup -1}. This method was successfully used for the determination of spiked uranium in natural water samples.

The system uranyl nitrate-dietyl ether-water. Extraction by water in spray and packed columns from uranyl nitrate-either solutions

International Nuclear Information System (INIS)

Perez Luina, A.; Gutierrez Jodra, L.

1960-01-01

This paper is a continuation of the one published in Chemical Engineering Progress. Symposium Series, 50, n. 12, 127 (1954). New runs for spray columns, are given and other concentrations in uranyl nitrate for the packed columns. New correlations for the overall H.T.U. are also given. The individual H.T.U. have been grapycally calculated and show that the film resistances have similar values, being independent of the concentration of the ether phase. (Author) 24 refs

Synthesis and crystal structure of hydrogen selenates K(HSeO4)(H2SeO4) and Cs(HSeO4)(H2SeO4)

International Nuclear Information System (INIS)

Troyanov, S.I.; Morozov, I.V.; Zakharov, M.A.; Kemnitz, E.

1999-01-01

Hydrogen selenates of the compositions K(HSeO 4 )(H 2 SeO 4 ) and Cs(HSeO 4 )(H 2 SeO 4 ) are synthesized by the reaction of alkali metal carbonates with an excess of the concentrated selenic acid. The X-ray diffraction study showed that both compounds are isostructural to the corresponding hydrogen sulfates. The difference in the systems of hydrogen bonding are caused by various combinations of the acceptor functions of the oxygen atoms in the HSeO 4 and H 2 SeO 4 groups

Infrared absorption spectra of selenate compounds of indium (3)

International Nuclear Information System (INIS)

Kharitonov, Yu.Ya.; Kadoshnikova, N.V.; Tananaev, I.V.

1979-01-01

Obtained and discussed are infrared absorption spectra (400-4000 cm -1 ) of the following indium selenates: In 2 (SeO 4 ) 3 x5H 2 O, In 2 (SeO 4 ) 3 x9H 2 O, NaIn(SeO 4 ) 2 x6H 2 O, NaIn(SeO 4 ) 2 xH 2 O, MIn(SeO 4 ) 2 x4H 2 O (M=NH 4 , K, Rb), CsIn(SeO 4 ) 2 x2H 2 O, Na 3 In(SeO 4 ) 3 x7H 2 O, MIn(SeO 4 ) 2 (M=NH 4 , Na, K, Rb, Cs), M 2 InOH(SeO 4 ) 2 xyH 2 O (M=NH 4 , Na, K, Rb) and K 2 InOD(SeO 4 ) 2 xyD 2 O

Interaction of uranyl ions with snake venom proteins from Lachesis muta muta

International Nuclear Information System (INIS)

MacCordick, H.J.; Taghva, F.

1997-01-01

The reaction product of uranyl nitrate with whole-protein Bushmaster snake venom in nitrate buffer at pH 3.5 has been studied. The maximum uptake of uranium was 291 μmol U x g -1 of venom. The infrared spectrum of the product showed an asymmetric O-U-O vibration at 921 cm -1 typical of complex formation with the uranyl ion. Stability measurements with the UO 2 2+ -protein complex in neutral medium indicated moderate hydrolytic stability, with 14% dissociation after 16 hours at 0 deg C. Neutron irradiation and desorption studies with a 235 U-labelled complex showed that generated fission products such as lanthanides and barium were readily lixiviated at pH 7, whereas Ru and Zr were highly retained by the protein substrate. (author)

Crystallization characteristics of ammonium uranyl carbonate (AUC) in ammonium carbonate solutions

International Nuclear Information System (INIS)

Kim, T.J.; Jeong, K.C.; Park, J.H.; Chang, I.S.; Choi, C.S.

1994-01-01

Ammonium carbonate solutions with an excessive amount of NH 3 were produced in a commercial AUC (ammonium uranyl carbonate) conversion plant. In this study the AUC crystals, precipitated with uranyl nitrate and ammonium carbonate solutions prepared in the laboratory, were characterized to determine the feasibility of recycling ammonium carbonate solution. The AUC crystals were easily agglomerated with the increasing concentration of CO 3 2- and mole ratio of NH 4 + /CO 3 2- in ammonium carbonate solution. Effects of a mixing system for the solution in the AUC crystallizer and the feed location of the solution onthe agglomeration of AUC crystals were also studied along with the effects of agglomerated AUC powders on UO 2 powders. Finally, the feasibility of manufacturing UO 2 fuel with a sintered pellet density of 10.52 g/cm 3 , using the AUC powders generated in this experiment, was demonstrated. (orig.)

Synthesis and investigation of uranyl molybdate UO2MoO4

International Nuclear Information System (INIS)

Nagai, Takayuki; Sato, Nobuaki; Kitawaki, Shin-ichi; Uehara, Akihiro; Fujii, Toshiyuki; Yamana, Hajimu; Myochin, Munetaka

2013-01-01

In order to examine easily synthetic conditions of uranyl molybdate, UO 2 MoO 4 , used for the reprocessing process study of spent nuclear oxide fuels in alkaline molybdate melts, the uranium molybdate compounds were produced from U 3 O 8 powder and anhydrous MoO 3 reagent. The results of having investigated them in solid state by using X-ray diffractometry and Raman spectrometry, it was confirmed that UO 2 MoO 4 could be synthesized by heating mixed powder of U 3 O 8 and MoO 3 with stoichiometric mole ratio at 770 °C for 4 h under air atmosphere. Moreover, adding this UO 2 MoO 4 into Li 2 MoO 4 -Na 2 MoO 4 eutectic melt, most of the dissolved uranium species in the melt were observed as hexa–valent uranyl ions by absorption spectrophotometry

Poly(organo phosphazene) nanoparticles surface modified with poly(ethylene oxide).

Science.gov (United States)

Vandorpe, J; Schacht, E; Stolnik, S; Garnett, M C; Davies, M C; Illum, L; Davis, S S

1996-10-05

The use of biodegradable derivatives of poly(organo phosphazenes) for the preparation of nanoparticles and their surface modification with the novel poly(ethylene oxide) derivative of poly(organo phosphazene) has been assessed using a range of in vitro characterization methods. The nanoparticles were produced by the precipitation solvent evaporation method from the derivative co-substituted with phenylalanine and glycine ethyl ester side groups. A reduction in particle size to less than 200 nm was achieved by an increase in pH of the preparation medium. The formation (and colloidal stability) of these nanoparticles seems to be controlled by two opposite effects: attractive hydrophobic interactions between phenylalanine ester groups and electrostatic repulsions arising from the carboxyl groups formed due to (partial) hydrolysis of the ester bond(s) at the high pH of the preparation medium. The poly[(glycine ethyl ester)phosphazene] derivative containing 5000-Da poly(ethylene oxide) as 5% of the side groups was used for the surface modification of nanoparticles. Adsorbed onto the particles, the polymer produced a thick coating layer of approximately 35 nm. The coated nanoparticles exhibited reduced surface negative potential and improved colloidal stability toward electrolyte-induced flocculation, relative to the uncoated system. However, the steric stabilization provided was less effective than that of a Poloxamine 908 coating. This difference in effectiveness of the steric stabilization might indicate that, although both the stabilizing polymers possess a 5000-Da poly(ethylene oxide) moiety, there is a difference in the arrangements of these poly(ethylene oxide) chains at the particle surface. (c) 1996 John Wiley & Sons, Inc.

Correlation between the structure and infra-red absorption characteristics of mono-deuterated compounds: contribution to the study of organo-magnesium compounds

International Nuclear Information System (INIS)

Paillous, A.

1965-10-01

The high sensitivity of the ν (C-D) vibration to the variations brought about by the substitution of the carbon attached to the deuterium is shown in the case of organic or organo-metallic mono-deuterated molecules. In particular, syntheses of various mono-deuterated organo-magnesium compounds have been carried out; results are given concerning an infra-red spectrometric examination of these compounds in the range 2100 - 2250 cm -1 . The results show the existence of only one type of deuterated carbon, which suggests that the same carbanion is involved in various ionic associations for the different magnesium-containing compounds. (authors) [fr

Effect of the temperature and oxalic acid in the uranyl sorption in zircon; Efecto de la temperatura y acido oxalico en la sorcion de uranilo en circon

Energy Technology Data Exchange (ETDEWEB)

Ordonez R, E.; Almazan T, M. G.; Garcia G, N. [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico); Hernandez O, R., E-mail: eduardo.ordonez@inin.gob.mx [Instituto Tecnologico de Veracruz, Ingenieria Quimica, Miguel Angel de Quevedo No. 2779, 91860 Veracruz (Mexico)

2012-10-15

In this work the results of the temperature effect study are presented on uranyl solutions adsorbed on zirconium silicate (ZrSiO{sub 4}) and also on the compounds formed in surface with oxalic acid. The adsorption isotherms of uranyl on hydrated zircon with NaClO{sub 4} 0.5 M, show an increase of the uranyl sorption efficiency when increasing the temperature from 20 to 4 C with a sudden descent in this efficiency when changing the temperature at 60 C. The uranyl sorption efficiency increases to hydrate the zircon with a solution of oxalic acid 0.1 M, maintaining the same tendency regarding to the temperatures of the sorption in medium NaClO{sub 4} 0.5 M. The complex formation in the zircon surface with organic acids of low molecular weight increases the fixation of the uranyl in solution due to the formation of ternary systems, in the order Zircon/A. Organic/Uranyl, without altering their response to the temperature. (Author)

Uranyl Photocleavage of Phosphopeptides Yields Truncated C-Terminally Amidated Peptide Products

DEFF Research Database (Denmark)

Elnegaard, Rasmus L B; Møllegaard, Niels Erik; Zhang, Qiang

2017-01-01

photocleavage reaction of a tetraphosphorylated β-casein model peptide. We show that the primary photocleavage products of the uranyl-catalysed reaction are C-terminally amidated. This could be of great interest to the pharmaceutical industry, as efficient peptide amidation reactions are one of the top...

Phylogenetic or environmental control on the organo-chemical composition of Sphagnum mosses?

Science.gov (United States)

Limpens, Juul; Nilsson, Mats

2014-05-01

Decomposition of organic material is one of the key processes that determines the size of the soil-feedback to global warming, but it is also a process surrounded with one of the largest uncertainties, making understanding its mechanistic drivers of crucial importance. In organic soils decomposition is closely determined by the organo-chemical composition of the litter entering the soil. But what, in turn drives the organo-chemical composition? Is it an emergent feature of the environment the species producing the litter grow in, or is it an evolutionary trait that can be tracked through the species' phylogeny? We set out to answer this question for one of the most import peat-forming plants on earth: the genus Sphagnum. We sampled 18 Sphagnum species, about equally distributed over 6 sites spanning a wide range of environmental conditions: most species were collected at multiple sites. For all species we characterised the chemical composition, focussing on three functional chemistry groups: (i) mineral elements, (ii) carbohydrate polymers (iii) non-carbohydrate polymers (aromatic and aliphatic compounds) . For each group of compounds we used multivariate statistical techniques to derive the degree of variation explained by environment: (site, position within site) and phylogeny (sections within genus Sphagnum). We found that the variation in mineral element concentrations was mostly explained by environment, with the biggest differences in the concentrations of basic cat-ions calcium and magnesium. In contrast, the variation in carbohydrates was mostly explained by phylogeny, with clear associations between sections and monosaccharides. The monosaccharide rhamnose was associated with species from the Acutifolia section known for their poor degradability, whereas xylose and galactose were closely associated with degradable species from the Cuspidata section. The composition non-carbohydrate polymers took an intermediate position: both environment and phylogeny

Uranyl phosphate mineral in Gapyeong area

International Nuclear Information System (INIS)

Chung, S.J.

1980-01-01

An uranyl phosphate crystal from Gapeong area is studied by means of single crystal x-ray diffraction and electron microscopic qualitative analysis of chemical contents. The crystal is identified as meta-ankoleite which has a unit cell of super structure with a=b=6.99 A, c=17.69 A and space group P4 2 22. There exists some indication in the total fluorescent spectrum of the sample that potassium may be partially substituted by calcium. The chemical formula of this meta-ankoleite may be expressed by Ksub(1-2x)Casub(x)(UO 2 PO 4 ) (H 2 O)sub(3-x). (Author)

Organo-layered double hydroxides composite thin films deposited by laser techniques

Energy Technology Data Exchange (ETDEWEB)

Birjega, R. [National Institute for Lasers, Plasma and Radiation Physics, 409 Atomistilor Str., 77125 Bucharest-Magurele (Romania); Vlad, A., E-mail: angela.vlad@gmail.com [National Institute for Lasers, Plasma and Radiation Physics, 409 Atomistilor Str., 77125 Bucharest-Magurele (Romania); Matei, A.; Dumitru, M.; Stokker-Cheregi, F.; Dinescu, M. [National Institute for Lasers, Plasma and Radiation Physics, 409 Atomistilor Str., 77125 Bucharest-Magurele (Romania); Zavoianu, R. [University of Bucharest, Faculty of Chemistry, Department of Chemical Technology and Catalysis, 4-12 Regina Elisabeta Bd., Bucharest 030018 (Romania); Raditoiu, V.; Corobea, M.C. [National R.& D. Institute for Chemistry and Petrochemistry, ICECHIM, 202 Splaiul Independentei Str., CP-35-274, 060021 Bucharest (Romania)

2016-06-30

Highlights: • PLD and MAPLE was successfully used to produce organo-layered double hydroxides. • The organic anions (dodecyl sulfate-DS) were intercalated in co-precipitation step. • Zn2.5Al-LDH (Zn/Al = 2.5) and Zn2.5Al-DS thin films obtained in this work could be suitable for further applications as hydrophobic surfaces. - Abstract: We used laser techniques to create hydrophobic thin films of layered double hydroxides (LDHs) and organo-modified LDHs. A LDH based on Zn-Al with Zn{sup 2+}/Al{sup 3+} ratio of 2.5 was used as host material, while dodecyl sulfate (DS), which is an organic surfactant, acted as guest material. Pulsed laser deposition (PLD) and matrix assisted pulsed laser evaporation (MAPLE) were employed for the growth of the films. The organic anions were intercalated in co-precipitation step. The powders were subsequently used either as materials for MAPLE, or they were pressed and used as targets for PLD. The surface topography of the thin films was investigated by atomic force microscopy (AFM), the crystallographic structure of the powders and films was checked by X-ray diffraction. FTIR spectroscopy was used to evidence DS interlayer intercalation, both for powders and the derived films. Contact angle measurements were performed in order to establish the wettability properties of the as-prepared thin films, in view of functionalization applications as hydrophobic surfaces, owing to the effect of DS intercalation.

Tritium gettering from air with hydrogen uranyl phosphate

International Nuclear Information System (INIS)

Souers, P.C.; Uribe, F.S.; Stevens, C.G.; Tsugawa, R.T.

1985-01-01

Hydrogen uranyl phosphate (HUP), a solid proton electrolyte, getters tritium gas and water vapor from air by DC electrical action. We have reduced the formation of residual tritiated water to less than 2%, and demonstrated that HUP can clean a 5.5 m 3 working glove box. Data are presented to illustrate the parameters of the gettering and a model is derived. Two other tritium gettering electrolytes have been discovered. 9 refs., 5 figs., 3 tabs

Investigation of stacked elemental layers for Cu(In,Ga)Se{sub 2} thin film preparation by rapid thermal selenization

Energy Technology Data Exchange (ETDEWEB)

Stroth, Christiane; Ohland, Joerg; Mikolajczak, Ulf; Madena, Thomas; Keller, Jan; Parisi, Juergen; Hammer, Maria; Riedel, Ingo [Energy and Semiconductor Research Laboratory, Department of Physics, University of Oldenburg, 26111 Oldenburg (Germany)

2013-07-01

Rapid thermal selenization of pure metallic (Cu-In-Ga) or selenium-containing (Cu-In-Ga-Se) precursors is a favorable method to fabricate Cu(In,Ga)Se{sub 2} absorber films for application in thin film solar cells. Because of its upscaling potential and the short process time it is a promising approach for the fabrication of CIGSe photovoltaic modules on industrial scale. As a preliminary work for prospective plasma-enhanced selenization of stacked elemental layers (SEL) the elements copper, indium and gallium were sequentially deposited on molybdenum coated soda-lime glass by thermal evaporation. The stacking order was varied and the precursors were annealed with different heating rates. Morphology, elemental depth distribution and phases of the layers were investigated before and after annealing using scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction. Furthermore the influence of different heating rates on phase transitions during annealing was studied by in-situ X-ray diffraction.

TG/DTA and X ray Diffraction Studies on Ammonium Uranyl Nitrate

International Nuclear Information System (INIS)

Kim, Byung Ho; Lee, Young Bum; Jeong, Ji Young; Choi, Jong Hyun; Kim, Tae Joon; Nam, Ho Yun; Kim, Jong Man

2011-01-01

Ammonium uranyl nitrate (AUN) is an important intermediate product during conversion of a uranyl nitrate[UO 2 (NO 3 ) 2 ] solution to UO 2 powder for the fabrication of nuclear fuels, the so-called modified direct denitration (MDD) process. The MDD process involves the thermal decomposition of AUN double salts, which are prepared from a mixture consisting of a UO 2 (NO 3 ) 2 solution and NH 4 NO 3 . The physical and chemical properties of an oxide powder depend upon its thermal treatment. Three double salts are known for the UO 2 (NO 3 ) 2 - NH 4 NO 3 -H 2 O system, but there have been only a few studies done on thermal decomposition of these salts. Therefore, the objective of this study is to investigate the reaction pathways during a thermal decomposition and reduction of AUN to achieve a better knowledge of the influence of an AUN preparation process and thermal decomposition procedures on uranium oxides under a nitrogen, air, or hydrogen atmosphere

Chromium(VI) sorption efficiency of acid-activated banana peel over organo-montmorillonite in aqueous solutions.

Science.gov (United States)

Ashraf, Anam; Bibi, Irshad; Niazi, Nabeel Khan; Ok, Yong Sik; Murtaza, Ghulam; Shahid, Muhammad; Kunhikrishnan, Anitha; Li, Dongwei; Mahmood, Tariq

2017-07-03

In the present study, we examined sorption of chromate (Cr(VI)) to acid-activated banana peel (AABP) and organo-montmorillonite (O-mont) as a function of pH, initial Cr(VI) concentration at a sorbent dose of 4 g L -1 and at 20 ± 1°C in aqueous solutions. In sorption edge experiments, maximum Cr(VI) removal was obtained at pH 3 after 2 hours by AABP and O-mont (88% and 69%). Sorption isotherm data showed that the sorption capacity of AABP was higher than O-mont (15.1 vs. 6.67 mg g -1 , respectively, at pH 4). Freundlich and Langmuir models provided the best fits to describe Cr(VI) sorption onto AABP (R 2 = 0.97) and O-mont (R 2 = 0.96). Fourier transform infrared spectroscopy elucidated that for AABP mainly the -OH, -COOH, -NH 2 , and for O-mont intercalated amines and -OH surface functional groups were involved in Cr(VI) sorption. The scanning electron microscopy combined with energy dispersive X-ray spectroscopy (SEM-EDX) analyses, although partly, indicate that the (wt. %) proportion of cations (e.g., Ca, Mg) in AABP decreased after Cr(VI) sorption. This may be due to ion exchange of chromite (Cr(III)) (produced from Cr(VI) reduction) with cationic elements in AABP. Also, Cr(VI) desorption (using phosphate solution) from AABP was lower (29%) than that from O-mont (51%) up to the third regeneration cycle. This bench scale comparative study highlights that the utilization of widely available and low-cost acid-activated biomaterials has a greater potential than organo-clays for Cr(VI) removal in aqueous media. However, future studies are warranted to precisely delineate different mechanisms of Cr(VI) sorption/reduction by acid-activated biomaterials and organo-clays.

Complexes of vanadyl and uranyl ions with the chelating groups of humic matter

International Nuclear Information System (INIS)

Goncalves, M.L.S.; Mota, A.M.

1987-01-01

The uranyl and vanadyl complexes formed with salicylic, phthalic and 3,4-dihydroxybenzoic acids have been studied by potentiometry in order to determine the stability constants of the Msub(m) Lsub(n) species formed in solution, and the constants for hydrolysis and polymeric complexes, at 25.0 0 , in 0.10, 0.40 and 0.70M sodium perchlorate. MINIQUAD was used in process the data to find the best models for the species in solution, and calculate the formation constants. The uranyl-salicylic acid sytem was also studied by spectrophotometry and the program SQUAD used to process the data obtained. The best models for these systems show that co-ordination of the uranyl ion by carboxylate groups is easier than for the vanadyl ion, whereas the vanadyl ion seems to form more stable complexes with phenolate groups. Both oxo-cations seem to tend to hydrolyse rather than form complexes when the L:M ratios are greater than unity. Although the change in the constants with ionic strength is small, the activity coefficients of the salicylate and phthalate species have been calculated at ionic strengths 0.40 and 0.70M, along with the interaction parameters with Na + , from the stability constants found for the species ML and H 2 L, according to the Bronsted-Guggenheim expression. (author)

Photochemical methodologies for organic waste treatment: advanced oxidation process using uranyl ion with H2O2

International Nuclear Information System (INIS)

Naik, D.B.; Sarkar, S.K.; Mukherjee, T.

2009-01-01

Excited uranyl ion is able to degrade dyes such as thionine and methylene blue on irradiation with 254 nm/300 nm light. By adding H 2 O 2 along with uranyl ion, photodegradation takes place with visible light and also with enhanced rate. The hydroxyl radicals generated in the reoxidation of U(IV)/UO 2 + to UO 2 2+ are responsible for this enhanced degradation. The above advanced oxidation process (AOP) was applied to study the oxidation of 2-propanol to acetone. (author)

The simulation of lunar gravity field recovery from D-VLBI of Chang’E-1 and SELENE lunar orbiters

Science.gov (United States)

Yan, Jianguo; Ping, Jingsong; Matsumoto, K.; Li, Fei

2008-07-01

The lunar gravity field is a foundation to study the lunar interior structure, and to recover the evolution history of the Moon. It is still an open and key topic for lunar science. For above mentioned reasons, it becomes one of the important scientific objectives of recent lunar missions, such as KAGUYA (SELENE) the Japanese lunar mission and Chang’E-1, the Chinese lunar mission. The Chang’E-1 and the SELENE were successfully launched in 2007. It is estimated that these two missions can fly around the Moon longer than 6 months simultaneously. In these two missions, the Chinese new VLBI (Very Long Baseline Interferometry) network will be applied for precise orbit determination (POD) by using a differential VLBI (D-VLBI) method during the mission period. The same-beam D-VLBI technique will contribute to recover the lunar gravity field together with other conventional observables, i.e. R&RR (Range and Range Rate) and multi-way Doppler. Taking VLBI tracking conditions into consideration and using the GEODYNII/SOVLE software of GSFC/NASA/USA [Rowlands, D.D., Marshall, J.A., Mccarthy, J., et al. GEODYN II System Description, vols. 1 5. Contractor Report, Hughes STX Corp. Greenbelt, MD, 1997; Ullman, R.E. SOLVE program: mathematical formulation and guide to user input, Hughes/STX Contractor Report, Contract NAS5-31760. NASA Goddard Space Flight Center, Greenbelt, Maryland, 1994], we simulated the lunar gravity field recovering ability with and without D-VLBI between the Chang’E-1 and SELENE main satellite. The cases of overlapped flying and tracking period of 30 days, 60 days and 90 days have been analyzed, respectively. The results show that D-VLBI tracking between two lunar satellites can improve the gravity field recovery remarkably. The results and methods introduced in this paper will benefit the actual missions.

Biosensing for the Environment and Defence: Aqueous Uranyl Detection Using Bacterial Surface Layer Proteins

Directory of Open Access Journals (Sweden)

David J.R. Conroy

2010-05-01

Full Text Available The fabrication of novel uranyl (UO22+ binding protein based sensors is reported. The new biosensor responds to picomolar levels of aqueous uranyl ions within minutes using Lysinibacillus sphaericus JG-A12 S-layer protein tethered to gold electrodes. In comparison to traditional self assembled monolayer based biosensors the porous bioconjugated layer gave greater stability, longer electrode life span and a denser protein layer. Biosensors responded specifically to UO22+ ions and showed minor interference from Ni2+, Cs+, Cd2+ and Co2+. Chemical modification of JG-A12 protein phosphate and carboxyl groups prevented UO22+ binding, showing that both moieties are involved in the recognition to UO22+.

PVC membrane based potentiometric sensor for uranyl ion using thenoyl trifluoro acetone as ionophore

International Nuclear Information System (INIS)

Nanda, D.; Chouhan, H.P.S.; Maiti, B.

2004-01-01

Uranyl ion selective electrode based on thenoyl trifluoro acetone (TTA) incorporated into a polyvinyl chloride (PVC) membrane has been developed where dibutyl phthalate and sodium tetraphenyl borate have been used as plasticizer and anion excluder respectively. The PVC membrane containing the active ionophore, TTA, and the other ingredients has been directly cast a graphite electrode. The electrode shows near Nernstian response to UO 2 2+ in the concentration range of 10 -1 to 10 -6 mol. L -1 an average slope of 30 mV/decade. Alkali and alkaline earth ions do not interfere with the determination of uranyl ion. Interference of transition metal ions and Th (IV) is eliminated using EDTA. (author)

Organo-Functionalization of Silicon Nanocrystals Synthesized by Inductively Coupled Plasma Chemical Vapor Deposition

Energy Technology Data Exchange (ETDEWEB)

Lee, Don-Sung; Choe, Dong-Hoe; Jeong, Hyun-Dam [Chonnam National University, Gwangju (Korea, Republic of); Yoo, Seung-Wan; Kim, Jung-Hyung [Korea Research Institute of Standards and Science, Daejeon (Korea, Republic of)

2016-05-15

Octadecyl-terminated silicon nanocrystals (ODE-Si NCs) are obtained via a surface-initiated thermal hydrosilylation reaction on hydride-terminated Si NCs (H-Si NCs). Pristine Si NCs were synthesized at the gram scale by using inductively coupled plasma chemical vapor deposition (ICP-CVD) . The H-Si NCs were produced through a chemical etching process with hydrofluoric acid (HF), ethanol (EtOH), and distilled water (d-H{sub 2}O). The results obtained from X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM) indicate that the synthesized Si NCs obtained via ICP-CVD have diamond cubic-structured silicon with a grain size of 10 nm and a densely packed Si NC array consisting of individual NCs. Organo-functionalized Si NCs, i.e., ODE-Si NCs, are well soluble in organic solvent whereas pristine Si NCs synthesized through ICP-CVD are not. The surface chemistry of the ODE-Si NCs was confirmed via Fourier transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance spectroscopy ({sup 1}H-NMR), and field emission transmission electron microscopy (FE-TEM). Thereby, these newly synthesized and scalable organo-functionalized Si NCs are applicable as raw materials for practical use in devices by tuning the surface chemistry with various capping molecules.

μOrgano: A Lego®-Like Plug & Play System for Modular Multi-Organ-Chips.

Directory of Open Access Journals (Sweden)

Peter Loskill

Full Text Available Human organ-on-a-chip systems for drug screening have evolved as feasible alternatives to animal models, which are unreliable, expensive, and at times erroneous. While chips featuring single organs can be of great use for both pharmaceutical testing and basic organ-level studies, the huge potential of the organ-on-a-chip technology is revealed by connecting multiple organs on one chip to create a single integrated system for sophisticated fundamental biological studies and devising therapies for disease. Furthermore, since most organ-on-a-chip systems require special protocols with organ-specific media for the differentiation and maturation of the tissues, multi-organ systems will need to be temporally customizable and flexible in terms of the time point of connection of the individual organ units. We present a customizable Lego®-like plug & play system, μOrgano, which enables initial individual culture of single organ-on-a-chip systems and subsequent connection to create integrated multi-organ microphysiological systems. As a proof of concept, the μOrgano system was used to connect multiple heart chips in series with excellent cell viability and spontaneously physiological beat rates.

μOrgano: A Lego®-Like Plug & Play System for Modular Multi-Organ-Chips.

Science.gov (United States)

Loskill, Peter; Marcus, Sivan G; Mathur, Anurag; Reese, Willie Mae; Healy, Kevin E

2015-01-01

Human organ-on-a-chip systems for drug screening have evolved as feasible alternatives to animal models, which are unreliable, expensive, and at times erroneous. While chips featuring single organs can be of great use for both pharmaceutical testing and basic organ-level studies, the huge potential of the organ-on-a-chip technology is revealed by connecting multiple organs on one chip to create a single integrated system for sophisticated fundamental biological studies and devising therapies for disease. Furthermore, since most organ-on-a-chip systems require special protocols with organ-specific media for the differentiation and maturation of the tissues, multi-organ systems will need to be temporally customizable and flexible in terms of the time point of connection of the individual organ units. We present a customizable Lego®-like plug & play system, μOrgano, which enables initial individual culture of single organ-on-a-chip systems and subsequent connection to create integrated multi-organ microphysiological systems. As a proof of concept, the μOrgano system was used to connect multiple heart chips in series with excellent cell viability and spontaneously physiological beat rates.

Crystal chemistry of uranyl carboxylate coordination networks obtained in the presence of organic amine molecules

Energy Technology Data Exchange (ETDEWEB)

Mihalcea, Ionut; Henry, Natacha; Loiseau, Thierry [Unite de Catalyse et Chimie du Solide (UCCS) - UMR CNRS 8181, Universite de Lille Nord de France, USTL-ENSCL, Villeneuve d' Ascq (France)

2014-03-15

Three uranyl isophthalates (1,3-bdc) and two uranyl pyromellitates (btec) of coordination-polymer type were hydrothermally synthesized (200 C for 24 h) in the presence of different amine-based molecules [1,3-diaminopropane (dap) or dimethylamine (dma) originating from the in situ decomposition of N,N-dimethylformamide]. (UO{sub 2}){sub 2}(OH){sub 2}(H{sub 2}O)(1,3-bdc).H{sub 2}O (1) is composed of inorganic tetranuclear cores, which are linked to each other through the isophthalato ligand to generate infinite neutral ribbons, which are intercalated by free H{sub 2}O molecules. The compounds (UO{sub 2}){sub 1.5}(H{sub 2}O)(1,3-bdc){sub 2}.0.5H{sub 2}dap.1.5H{sub 2}O (2) and UO{sub 2}(1,3-bdc){sub 1.5}.0.5H{sub 2}dap.2H{sub 2}O (3) consist of discrete uranyl-centered hexagonal bipyramids connected to each other by a ditopic linker to form a single-layer network for 2 or a double-layer network for 3. The protonated diamine molecules are located between the uranyl-organic sheets and balance the negative charge of the layered sub-networks. The phase (UO{sub 2}){sub 2}O(btec).2Hdma.H{sub 2}O (4) presents a 2D structure built up from tetranuclear units, which consist of two central sevenfold coordinated uranium centers and two peripheral eightfold coordinated uranium centers. The connection of the resulting tetramers through the pyromellitate molecules generates an anionic layerlike structure, in which the protonated dimethylammonium species are inserted. The compound UO{sub 2}(btec).2Hdma (5) is also a lamellar coordination polymer, which contains isolated eightfold coordinated uranium cations linked through pyromellitate molecules and intercalated by protonated dimethylammonium species. In both phases 4 and 5, the btec linker has non-bonded carboxyl oxygen atoms, which preferentially interact with the protonated amine molecules through a hydrogen-bond network. The different illustrations show the structural diversity of uranyl-organic coordination polymers with organic

Calorimetric measurement of the enthalpy of extraction of uranyl nitrate by tri-n-amyl phosphate

International Nuclear Information System (INIS)

Srinivasan, T.G.; Vasudeva Rao, P.R.; Venugopal, V.; Sood, D.D.

2002-01-01

Enthalpy of extraction of uranyl nitrate by tri n-amyl phosphate (TAP) and its solutions in n-dodecane has been directly measured by solution calorimetry for the first time. Measurements have been made at 303±1 K, in both forward as well as the reverse extraction modes. The enthalpies of the accompanying reactions such as the dilution of the uranyl nitrate in the aqueous phase, the hydration of TAP, the mixing of TAP and n-dodecane, the mixing of the metal-solvate (UO 2 (NO 3 ) 2 ·2TAP) and n-dodecane and mixing of the metal-solvate and TAP have also been independently measured and used to derive both the equilibrium state enthalpies and the standard state enthalpies for the extraction. Two distinct standard states have been used for the organic phase, viz., 1) all solutes infinitely diluted in diluent (ΔH*) and 2) all solutes infinitely diluted in the water saturated extractant (ΔH 0 ). The results have been compared with the enthalpies of extraction measured by employing the temperature dependence of the distribution ratio as well as calorimetry reported in the literature for extraction of uranyl nitrate by TAP and TBP. (author)

Structural evolution of a uranyl peroxide nano-cage fullerene: U60, at elevated pressures

Science.gov (United States)

Turner, K. M.; Lin, Y.; Zhang, F.; McGrail, B.; Burns, P. C.; Mao, W. L.; Ewing, R. C.

2015-12-01

U60 is a uranyl peroxide nano-cage that adopts a highly symmetric fullerene topology; it is topologically identical to C60. Several studies on the aqueous-phase of U60 clusters, [UO2(O2)(OH)]6060-, have shown its persistence in complex solutions and over lengthy time scales. Peroxide enhances corrosion of nuclear fuel in a reactor accident-uranyl peroxides often form near contaminated sites. U60 (Fm-3) crystallizes with approximate formula: Li68K12(OH)20[UO2(O2)(OH)]60(H2O)310. Here, we have used the diamond anvil cell (DAC) to examine U60 to understand the stability of this cluster at high pressures. We used a symmetric DAC with 300 μm culet diamonds and two different pressure-transmitting media: a mixture of methanol+ethanol and silicone oil. Using a combination of in situ Raman spectroscopy and synchrotron XRD, and electrospray ionization mass spectroscopy (ESI-MS) ex situ, we have determined the pressure-induced evolution of U60. Crystalline U60 undergoes an irreversible phase transition to a tetragonal structure at 4.1 GPa, and irreversibly amorphizes at 13 GPa. The amorphous phase likely consists of clusters of U60. Above 15 GPa, the U60 cluster is irreversibly destroyed. ESI-MS shows that this phase consists of species that likely have between 10-20 uranium atoms. Raman spectroscopy complements the diffraction measurements. U60 shows two dominant vibrational modes: a symmetric stretch of the uranyl U-O triple bond (810 cm-1), and a symmetric stretch of the U-O2-U peroxide bond (820 cm-1). As pressure is increased, these modes shift to higher wavenumbers, and overlap at 4 GPa. At 15 GPa, their intensity decreases below detection. These experiments reveal several novel behaviors including a new phase of U60. Notably, the amorphization of U60 occurs before the collapse of its cluster topology. This is different from the behavior of solvated C60 at high pressure, which maintains a hcp structure up to 30 GPa, while the clusters disorder. These results suggest

Gamma-radiation and isotopic effect on the critical behavior in triglycine selenate crystals

Science.gov (United States)

Kassem, M. E.; Hamed, A. E.; Abulnasr, L.; Abboudy, S.

1994-11-01

Isotopic effects in pure and γ-irradiated triglycine selenate crystals were investigated using the specific heat ( Cp) technique. The obtained results showed an interesting dependence of the critical behavior of Cp on the deuterium content. With increasing content of deuterium, the character of the phase transition changed from a second order (γ-type) to a first order transition. After γ-irradiation, the behavior of Cp around the phase transition region was essentially affected. The transition temperature, Tc, decreased and Δ Cp depressed, and the transition became broad. It was noted that the effect of γ-irradiation is opposite to the isotopic effect.

Removal of toxic uranium from synthetic nuclear power reactor effluents using uranyl ion imprinted polymer particles.

Science.gov (United States)

Preetha, Chandrika Ravindran; Gladis, Joseph Mary; Rao, Talasila Prasada; Venkateswaran, Gopala

2006-05-01

Major quantities of uranium find use as nuclear fuel in nuclear power reactors. In view of the extreme toxicity of uranium and consequent stringent limits fixed by WHO and various national governments, it is essential to remove uranium from nuclear power reactor effluents before discharge into environment. Ion imprinted polymer (IIP) materials have traditionally been used for the recovery of uranium from dilute aqueous solutions prior to detection or from seawater. We now describe the use of IIP materials for selective removal of uranium from a typical synthetic nuclear power reactor effluent. The IIP materials were prepared for uranyl ion (imprint ion) by forming binary salicylaldoxime (SALO) or 4-vinylpyridine (VP) or ternary SALO-VP complexes in 2-methoxyethanol (porogen) and copolymerizing in the presence of styrene (monomer), divinylbenzene (cross-linking monomer), and 2,2'-azobisisobutyronitrile (initiator). The resulting materials were then ground and sieved to obtain unleached polymer particles. Leached IIP particles were obtained by leaching the imprint ions with 6.0 M HCl. Control polymer particles were also prepared analogously without the imprint ion. The IIP particles obtained with ternary complex alone gave quantitative removal of uranyl ion in the pH range 3.5-5.0 with as low as 0.08 g. The retention capacity of uranyl IIP particles was found to be 98.50 mg/g of polymer. The present study successfully demonstrates the feasibility of removing uranyl ions selectively in the range 5 microg - 300 mg present in 500 mL of synthetic nuclear power reactor effluent containing a host of other inorganic species.

Studying of the dehydration process of uranyl nitrate hexahydrate (Unh)

International Nuclear Information System (INIS)

Badalov, A.; Kamalov, J.J.; Homidov, B.J.; Mirsaidov, I.U.; Eshbekov, N.R.

2005-01-01

By the tensimeteric method is studying the dehydration process of uranyl nitrate hexahydrate (Unh). It is shown, that the temperature interval 300-400 K in equilibrium conditions the dehydration process of Unh runs in three stages. According to the equations of dependence of saturated steam pressure from temperature, the thermodynamic characteristics of each stage of the dehydration process of Unh are calculated

Crystal structure of the (REE)-uranyl carbonate mineral kamotoite-(Y)

Czech Academy of Sciences Publication Activity Database

Plášil, Jakub; Petříček, Václav

2017-01-01

Roč. 81, č. 3 (2017), s. 653-660 ISSN 0026-461X R&D Projects: GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : kamotoite-(Y) * uranyl carbonate * rare-earth elements * crystal structure Subject RIV: DB - Geology ; Mineralogy OBOR OECD: Geology Impact factor: 1.285, year: 2016

Surface analysis of uranyl fluoride layers with a glow discharge lamp

International Nuclear Information System (INIS)

Nel, J.T.; Stander, C.M.; Boehmer, R.G.

1991-01-01

Surface analysis with a Grimm-type glow discharge lamp was used to analyse uranyl fluoride layers that had formed on a nickel substrate after exposure to UF 6 . Narrow-band optical filters were used to isolate the intensities of three fluorine emission lines. An in-depth profile of layer composition was obtained. (author)

Community ecology of the metazoan parasites of Atlantic Moonfish, Selene setapinnis (Osteichthyes: Carangidae from the coastal zone of the state of Rio de Janeiro, Brazil

Directory of Open Access Journals (Sweden)

A. S. Cordeiro

Full Text Available Eighty-nine specimens of Selene setapinnis (Mitchill, 1815 collected from the coastal zone of the State of Rio de Janeiro (21-23ºS, 41-45ºW and 23º05'S, 44º30'W, Brazil, from August 2001 to May 2002, were necropsied to study their metazoan parasites. Eighty-one (91% specimens of S. setapinnis were parasitized by one or more metazoan species. Twenty-one species of parasites were collected: 8 digeneans, 3 monogeneans, 2 cestodes, 5 nematodes, and 3 copepods. The endoparasites (digeneans, cestodes, and nematodes were 74.1% of total number of parasite specimens collected. The monogenean Pseudomazocraes selene (Hargis, 1957 was the most dominant species with the highest prevalence in the parasite community of S. setapinnis. The metazoan parasites of this host species showed the typical aggregated pattern of distribution. Only one parasite species (Acanthocolpoides pauloi Travassos, Freitas & Buhrnheim, 1955 showed positive correlation between the host total length and parasite abundance in S. setapinnis. Caligus robustus Bassett-Smith, 1898, P. selene, and Terranova sp. demonstrated positive correlation between the host total length and prevalence. Larvae of Terranova sp. showed influence of the host sex on its prevalence. A pair of ectoparasite species, P. selene-C. robustus, exhibited positive covariation between their abundances. Two pairs of endoparasite species, L. microstomum-P. merus and A. pauloi-P. merus showed significant covariation among their abundances; and the pair Terranova sp.-Raphidascaris sp. had positive co-ocorrence and covariation in the infracommunities of S. setapinnis. Like the parasite communities of the other carangid fishes from Rio de Janeiro, the parasite community of S. setapinnis is apparently only a slightly ordered species complex, characterized by dominance of endoparasite species.

Interfacial tension in systems involving TBP in dodecane, nitric acid, uranyl nitrate and water

International Nuclear Information System (INIS)

Kolarik, Z.; Pipkin, N.

1982-08-01

The interfacial tension was measured at 25 0 C in the systems TBP - n-dodecane/nitric acid - water and TBP - n-dodecane/nitric acid - uranyl nitrate - water. Empirical equations describing the interfacial tension as a function of the concentration of TBP in the starting organic phase and of uranium-(VI) and nitric acid in the equilibrium aqueous phase were suggested. In the absence of uranium (VI), the interfacial tension can also be correlated with the concentration of water in the equilibrium organic phase. Free TBP, hydrated or nonhydrated, and hydrated TBP solvates of nitric acid are interfacially active. Anhydrous TBP solvates of nitric acid and the TBP solvate of uranyl nitrate, which neither is hydrated, do not exhibit any visible interfacial activity. (orig.) [de

Thermal decomposition of uranyl nitrate hexahydrate. Study of intermediate reaction products; Decomposition thermique du nitrate d'uranyle hexahydrate etude des intermediaires de cette decomposition

Energy Technology Data Exchange (ETDEWEB)

Chottard, G [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1970-07-01

The thermal decomposition of uranyl nitrate hexahydrate has been carried but at constant pressure and constant rate of reaction. The following intermediary products have been shown to exist and isolated: UO{sub 2}(NO{sub 3}){sub 2}.3H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2}. 2H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2}. H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2} and UO{sub 3}. These products, together with the hexahydrate UO{sub 2} (NO{sub 3}){sub 2}.6H{sub 2}O, have been studied by: - X-ray diffraction, using the Debye-Scherrer method.- infra-red spectrography: determination of the type of bonding for the water and the nitrate groups. - nuclear magnetic resonance: study of the mobility of water molecules. The main results concern: - the water molecule bonds in the series of hydrates with 6.3 and 2 H{sub 2}O. - isolation and characterization of uranyl nitrate monohydrate, together with the determination of its molecular structure. - the mobility of the water molecules in the series of the hydrates with 6.3 and 2 H{sub 2}O. An analysis is made of the complementary results given by infra-red spectroscopy and nuclear magnetic resonance; they are interpreted for the whole of the hydrate series. [French] La decomposition thermique du nitrate d'uranyle hexahydrate a ete effectuee en operant a pression et vitesse de decomposition constantes. Les produits intermediaires suivants ont ete mis en evidence et isoles: UO{sub 2}(NO{sub 3}){sub 2}, 3H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2}, 2H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2},H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2} et UO{sub 3}. Ces composes, ainsi que l'hexahydrate UO{sub 2}(NO{sub 3} ){sub 2}, 6H{sub 2}O ont ete etudies par: - diffraction des rayons X, selon la methode Debye-Scherrer.- spectrographie infra-rouge: determination des modes de liaison de l'eau et des groupements nitrate. - resonance magnetique nucleaire: etude de la mobilite des molecules d'eau. Les principaux resultats portent sur: - les liaisons des molecules d'eau dans la

Water- and organo-dispersible gold nanoparticles supported by using ammonium salts of hyperbranched polystyrene: preparation and catalysis.

Science.gov (United States)

Gao, Lei; Nishikata, Takashi; Kojima, Keisuke; Chikama, Katsumi; Nagashima, Hideo

2013-12-01

Gold nanoparticles (1 nm in size) stabilized by ammonium salts of hyperbranched polystyrene are prepared. Selection of the R groups provides access to both water- and organo-dispersible gold nanoparticles. The resulting gold nanoparticles are subjected to studies on catalysis in solution, which include reduction of 4-nitrophenol with sodium borohydride, aerobic oxidation of alcohols, and homocoupling of phenylboronic acid. In the reduction of 4-nitrophenol, the catalytic activity is clearly dependent on the size of the gold nanoparticles. For the aerobic oxidation of alcohols, two types of biphasic oxidation are achieved: one is the catalyst dispersing in the aqueous phase, whereas the other is in the organic phase. The catalysts are reusable more than four times without loss of the catalytic activity. Selective synthesis of biphenyl is achieved by the homocoupling of phenylboronic acid catalyzed by organo-dispersible gold nanoparticles. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microporous uranyl chromates successively formed by evaporation from acidic solution

Energy Technology Data Exchange (ETDEWEB)

Siidra, Oleg I.; Nazarchuk, Evgeny V.; Bocharov, Sergey N.; Kayukov, Roman A. [St. Petersburg State Univ. (Russian Federation). Dept. of Crystallography; Depmeier, Wulf [Kiel Univ. (Germany). Inst. fuer Geowissenschaften

2018-04-01

The first microporous framework structures containing uranium and chromium have been synthesized and characterized. Rb{sub 2}[(UO{sub 2}){sub 2}(CrO{sub 4}){sub 3}(H{sub 2}O){sub 2}](H{sub 2}O){sub 3} (1) was crystallized from uranyl chromate solution by evaporation. Further evaporation led to increased viscosity of the solution and overgrowing of Rb{sub 2}[(UO{sub 2}){sub 2}(CrO{sub 4}){sub 3}(H{sub 2}O)](H{sub 2}O) (2) on the crystals of 1. With respect to 1, the framework of 2 is partially dehydrated. Both frameworks differ compositionally by only one water molecule, but this seemingly small difference affects significantly the pore size and overall structural topology of the frameworks, which present very different flexibility of the U-O-Cr links. These are rigid in the pillared framework of 1, in contrast to 2 where the U-O-Cr angles range from 126.3 to 168.2 , reflecting the substantial flexibility of Cr-O-U connections which make them comparable to the corresponding Mo-O-U links in uranyl molybdates.

The uranyl influence on a mutation process in germ and somatic cells of mice

International Nuclear Information System (INIS)

Kostrova, L.N.; Mosseh, I.B.; Molofej, V.P.

2008-01-01

The mutagenic effect of uranyl was revealed by the chromosome rearrangement test in germ and somatic cells of mice. The effect value depended on duration of substance administration into organism. (authors)

Behind adhesion of uranyl onto montmorillonite surface: A molecular dynamics study

Energy Technology Data Exchange (ETDEWEB)

Yang, W.; Zaoui, A., E-mail: azaoui@polytech-lille.fr

2013-10-15

Highlights: • We investigated the adsorption of uranyl onto Montmorillonite surface. • We studied the surface energy between layered Montmorillonite sheets. • We studied the work of adhesion between radionuclide and charged Montmorillonite. -- Abstract: We have performed molecular dynamics simulations to investigate the adsorption of radionuclide elements species onto substituted Montmorillonite (001) surface in the presence of different counterions. The structure and the dynamics of uranyl ion as well as its aquo, chloride ion, and carbonate complexes are analyzed. In addition, we have studied the surface energy between layered Montmorillonite sheets and the work of adhesion between radionuclide and charged Montmorillonite. The clay model used here is a Wyoming-type Montmorillonite with 0.75e negative charge per unit cell resulting from substitutions in Octahedral and Tetrahedral sheets. The system model was constructed based on CLAYFF force field potential model. To evaluate the thermodynamic work of adhesion, each surface and clay layer regions are converted to a thin film model. One and two species of radionuclide elements (UO{sub 2}(H{sub 2}O){sub 5},UO{sub 2}CO{sub 3}(H{sub 2}O){sub 5}, and UO{sub 2}Cl{sub 2}(H{sub 2}O){sub 5}) were deposited near the clay surface in a pseudo-two-dimensional periodic cell. Analysis shows that the uranyl ion structure is preserved with two axial oxygen atoms detected at 1.8 Å. Radial distribution functions results indicate that average U-O{sub w} distances are 2.45–2.61 Å, and 2.29–2.40 Å for U-O{sub c} distance. Average U-Cl distances are 2.78–3.08 Å, which is relatively larger than that of Uranium atom-Oxygen atom because of electrostatic factors.

A new uranyl phosphate sheet in the crystal structure of furongite

Energy Technology Data Exchange (ETDEWEB)

Dal Bo, Fabrice; Hatert, Frederic [Liege Univ. (Belgium). Lab. de Mineralogie; Philippo, Simon [Musee National d' Historie Naturelle, Luxembourg (Luxembourg). Section Mineralogie

2017-06-15

The crystal structure of furongite, Al{sub 4}[(UO{sub 2}){sub 4}(PO{sub 4}){sub 6}](OH){sub 2}(H{sub 2}O){sub 19.5}, from the Kobokobo pegmatite, Kivu, Democratic Republic of Congo, was solved for the first time. Furongite is triclinic, the space group P anti 1, Z=2, a = 12.1685(8), b = 14.1579(6), c = 17.7884(6) Aa, α = 79.822(3), β = 77.637(4), γ = 67.293(2) , and V = 2746.2(2)Aa{sup 3}. The crystal structure was refined from single crystal X-ray diffraction data to R{sub 1} = 0.0733 for 7716 unique observed reflections, and to wR{sub 2} = 0.2081 for all 12,538 unique reflections. The structure of furongite contains infinite uranyl phosphate sheets of composition [(UO{sub 2}){sub 4}(PO{sub 4}){sub 6}]{sup 10-} which are parallel to (1 0 1). The sheets are constituted by UrO{sub 5} pentagonal bipyramids and PO{sub 4} tetrahedra which share edges and vertices, and adjacent sheets are linked by a dense network of hydrogen bonds. Running through the sheets and connected mainly to the free apical oxygen atom of PO4 tetrahedra are Al octahedra connected together to form remarkable Al{sub 2}O{sub 5}(OH)(H{sub 2}O){sub 5} and Al{sub 4}O{sub 8}(OH){sub 2}(H{sub 2}O){sub 10} clusters. These Al clusters are only bonded to one sheet, and do not connect two adjacent sheets together. The topology of the uranyl phosphate sheets is related to the uranophane anion topology, and can be described as a new geometrical isomer of the uranophane group. Furongite is the first uranyl phosphate reported in nature with a U:P ratio of 2:3.

Weathering of natural uranyl oxide hydrates: Schoepite polytypes and dehydration effects

International Nuclear Information System (INIS)

Finch, R.J.; Miller, M.L.; Ewing, R.C.

1992-01-01

Partial dehydration of schoepite, UO 3 x2H 2 O, is reported to produce three discrete schoepite polytypes with characteristic unit cell parameters, but this has not been confirmed. The loss of structural water from the schoepite interlayer results in progressive modification to the structure; expansion parallel to schoepite cleavage planes, and extensive fracturing. Dehydration of schoepite commences at grain boundaries and progresses inward until the entire grain is converted to dehydrated schoepite, UO 3 x0.8H 2 O. The volume decrease associated with dehydration results in expanded grain boundaries. These gaps can provide pathways for the access of groundwater, and uranyl silicates and uranyl carbonates have precipitated within these gaps, replacing both schoepite and dehydrated schoepite. Schoepite, however, is not observed to re-precipitate where in contact with dehydrated schoepite. Thus, while the formation of schoepite early during the corrosion of uraninite may be favored, schoepite is not a long-term solubility limiting phase for oxidized uranium in natural ground waters containing dissolved silica or carbonate. (orig.)

Purification of Effluent from the Groundwood Production by Organo-zeolite

Directory of Open Access Journals (Sweden)

Anić-Vučinić, A.

2008-11-01

Fig. 1B the pertaining zeta potentials of the samples are shown. HDTMA cations were essentially quantitatively taken up by the clinoptilolite tuff up to loading level of L = 0.204 mmol g-1-(Fig. 1A. The results of the zeta potential measurements show that the negative surface charge changed to positive after modification with surfactant solutions (Fig. 1B. HDTMA cations form a stable organophilic coating on the clinoptilolite surface, and above surfactant loading level of 0.110 mmol g-1(isoelectric point, a second layer of HDTMA+ cations reverses the surface charge into positive. The optimal mass concentration of coagulant AlCl3·6H2O for the tested wastewater is γ = 0.8 g dm-1(Figs. 2A and 2B. Zeta potential of the solution above sediment received by coagulation with AlCl3·6H2O of mass concentration γ= 0.8 g dm-3 is ζ= -3.92 mV. The efficiency of removing the turbidity (Table 1 and COD is η = 67 % (from 799 to 263 NTU and 54% (from 13 200 to 6 040 mg dm-3. The efficiency of removing solved organic carbon and colour is significantlylesser: 22.7% (from 3010 to 2322 mg dm-3 and η = 33.0 % (from 681 to 457 Pt Co. By processing the solutions received after coagulation with AlCl3·6H2O of mass concentration of 0.8 g dm-3, with natural tuff and organo-zeolites whose loading are: 0.074; 0.123; 0.164 and 0.204 mmol g-1 HDTMA, TOC was decreased from γ=2322 mg dm-3 to the following: γ=2042, 1976, 1945, 1907 and 1821 mg dm-3 and was sorbed: q = 28.0; 34.6; 37.7; 41.5; and 50.1 mg g-1 TOC (Fig. 3A. Using the sample of organo-zeolite with loading of 0.204 mmol g-1 HDTMA, the efficiency of removing the organic carbon was improved from η= 22.7 % to 40.0 %. The efficiency of discolouring the tested solutions also increases with the change of the surface charge of organo-zeolites from negative to positive(Fig. 3B. The efficiency of removing the colour by using the natural tuff was improved from η= 33.0 % to η = 40.0 %, and by using the organo-zeolite with loading of L = 0

Rover exploration on the lunar surface; a science proposal for SELENE-B mission

Science.gov (United States)

Sasaki, S.; Kubota, T.; Akiyama, H.; Hirata, N.; Kunii, Y.; Matsumoto, K.; Okada, T.; Otake, M.; Saiki, K.; Sugihara, T.

LUNARSURFACE:ASCIENCES. Sasaki (1), T. Kubota (2) , H. Akiyama (1) , N. Hirata (3), Y. Kunii (4), K. Matsumoto (5), T. Okada (2), M. Otake (3), K. Saiki (6), T. Sugihara (3) (1) Department of Earth and Planetary Science, Univ. Tokyo, (2) Institute of Space and Astronautical Sciences, (3) National Space Development Agency of Japan, (4) Department of Electrical and Electronic Engineering, Chuo Univ., (5) National Aerospace Laboratory of Japan, (6) Research Institute of Materials and Resources, Akita Univ. sho@eps.s.u -tokyo.ac.jp/Fax:+81-3-5841-4569 A new lunar landing mission (SELENE-B) is now in consideration in Japan. Scientific investigation plans using a rover are proposed. To clarify the origin and evolution of the moon, the early crustal formation and later mare volcanic processes are still unveiled. We proposed two geological investigation plans: exploration of a crater central peak to discover subsurface materials and exploration of dome-cone structures on young mare region. We propose multi-band macro/micro camera using AOTF, X-ray spectrometer/diffractometer and gamma ray spectrometer. Since observation of rock fragments in brecciaed rocks is necessary, the rover should have cutting or scraping mechanism of rocks. In our current scenario, landing should be performed about 500m from the main target (foot of a crater central peak or a cone/dome). After the spectral survey by multi-band camera on the lander, the rover should be deployed for geological investigation. The rover should make a short (a few tens meter) round trip at first, then it should perform traverse observation toward the main target. Some technological investigations on SELENE-B project will be also presented.

Impact of uranyl-calcium-carbonato complexes on uranium(VI) adsorption to synthetic and natural sediments.

Science.gov (United States)

Stewart, Brandy D; Mayes, Melanie A; Fendorf, Scott

2010-02-01

Adsorption on soil and sediment solids may decrease aqueous uranium concentrations and limit its propensity for migration in natural and contaminated settings. Uranium adsorption will be controlled in large part by its aqueous speciation, with a particular dependence on the presence of dissolved calcium and carbonate. Here we quantify the impact of uranyl speciation on adsorption to both goethite and sediments from the Hanford Clastic Dike and Oak Ridge Melton Branch Ridgetop formations. Hanford sediments were preconditioned with sodium acetate and acetic acid to remove carbonate grains, and Ca and carbonate were reintroduced at defined levels to provide a range of aqueous uranyl species. U(VI) adsorption is directly linked to UO(2)(2+) speciation, with the extent of retention decreasing with formation of ternary uranyl-calcium-carbonato species. Adsorption isotherms under the conditions studied are linear, and K(d) values decrease from 48 to 17 L kg(-1) for goethite, from 64 to 29 L kg (-1) for Hanford sediments, and from 95 to 51 L kg(-1) for Melton Branch sediments as the Ca concentration increases from 0 to 1 mM at pH 7. Our observations reveal that, in carbonate-bearing waters, neutral to slightly acidic pH values ( approximately 5) and limited dissolved calcium are optimal for uranium adsorption.

Structural determination of some uranyl compounds by vibrational spectroscopy

International Nuclear Information System (INIS)

Rodriguez S, A.; Martinez Q, E.

1990-07-01

The vibrational spectra of different uranyl compounds has been studied and of it spectral information has been used the fundamental asymmetric vibrational frequency, to determine the length and constant bond force U=O by means of the combination of the concept of absorbed energy and the mathematical expression of Badger modified by Jones. It is intended a factor that simplifies the mathematical treatment and the results are compared with the values obtained for other methods. (Author)

Preconcentration of gold ions from water samples by modified organo-nanoclay sorbent prior to flame atomic absorption spectrometry determination

Energy Technology Data Exchange (ETDEWEB)

Afzali, Daryoush, E-mail: daryoush_afzali@yahoo.com [Nanochemistry Department, Research Institute of Environmental Sciences, International Center for Science, High Technology and Environmental Sciences, Kerman (Iran, Islamic Republic of); Mostafavi, Ali [Chemistry Department, Shahid Bahonar University of Kerman, Kerman (Iran, Islamic Republic of); Mirzaei, Mohammad [Nanochemistry Department, Research Institute of Environmental Sciences, International Center for Science, High Technology and Environmental Sciences, Kerman (Iran, Islamic Republic of); Chemistry Department, Shahid Bahonar University of Kerman, Kerman (Iran, Islamic Republic of)

2010-09-15

In this work, the applicability of modified organo nanoclay as a new and easy prepared solid sorbent for the preconcentration of trace amounts of Au(III) ion from water samples is studied. The organo nanoclay was modified with 5-(4'-dimethylamino benzyliden)-rhodanine and used as a sorbent for separation of Au(III) ions. The sorption of gold ions was quantitative in the pH range of 2.0-6.0. Quantitative desorption occurred with 6.0 mL of 1.0 mol L{sup -1} Na{sub 2}S{sub 2}O{sub 3}. The amount of eluted Au(III) was measured using flame atomic absorption spectrometry. In the initial solution the linear dynamic range was in the range of 0.45 ng mL{sup -1} to 10.0 {mu}g mL{sup -1}, the detection limit was 0.1 ng mL{sup -1} and the preconcentration factor was 105. Also, the relative standard deviation was {+-}2.3% (n = 8 and C = 2.0 {mu}g mL{sup -1}) and the maximum capacity of the sorbent was 3.9 mg of Au(III) per gram of modified organo nanoclay. The influences of the experimental parameters including sample pH, eluent volume and eluent type, sample volume, and interference of some ions on the recoveries of the gold ion were investigated. The proposed method was applied for preconcentration and determination of gold in different samples.

Modeling of critical experiments employing Raschig rings in uranyl nitrate solution

International Nuclear Information System (INIS)

Tanner, J.E.

1989-01-01

Four critical experiments employing borated glass rings in concentrated uranyl nitrate solution yielded k eff higher by 0. 04 when modeled with a flux-weighted, homogenized cross section set than when modeled with discrete rings. k eff varied by 0.014 for a 10% boron uncertainty and by up to 0.04 for a 10% packing fraction uncertainty

Application of membrane LaF3 electrode in the determination of stability constants of Uranyl Fluoride complex in solution

International Nuclear Information System (INIS)

Muzakky; Iswani GS; Mintolo

1996-01-01

A membrane electrode LaF 3 has been applied in the determination of uranyl fluoride complex stability constant in solution. The determination is based on the detection of free F ion in solution as a result of hydrolysis reaction (process) of uranyl ions into the uranyl hydroxide form at low pH. The experiment results showed that there was no effect of ammonium carbonate 2 M titran, flow rate on the electrode response. The F release is optimum at pH 1. The free F ion in solution is calculated from the standard curve at pH 1, after the fluoride concentration at the same pH has been corrected. Using the plot of average number of ligand binding (n) versus minus log of free ligand (-log F) the value of β1 = 4.4, β2 = 7.48, β3=9.73, and β4 = 11.67

Sorption of radioiodine in organo-clays and -soils

International Nuclear Information System (INIS)

Bors, J.

1990-01-01

In the framework of investigations on the sorption of radioiodine to natural and artificially altered soil components, a number of clay minerals and natural soils were treated with quaternary alkylammonium ions to replace the exchangeable metal cations. With help of batch experiments the resulting organo-clays were tested with respect to their sorption capability of radioiodine quantified by the distribution ratio (R D -value). Treatment of bentonite, vermiculite and cretaceous clay as well as of samples from natural horizons of chernozem soil with hexadecylpyridinium (HDPY + ) and benzethonium (BE + ) exhibited sorptions rates and amounts, which are several orders of magnitude higher than those of the respective untreated samples. Moderate increases of the R D -values were found after cation exchange with hexadecyltrimethylammonium (HDTMA + ), while the applications of trimethylphenylammonium (TMPA + ) and tetramethylammonium (TMA + ) were ineffective. Considerable sorption of radioiodine was observed with the commercially available Bentone. (orig.)

Gamma-radiation and isotopic effect on the critical behavior in triglycine selenate crystals

International Nuclear Information System (INIS)

Kassem, M.E.; Hamed, A.E.; Abulnasr, L.; Abboudy, S.

1994-01-01

Isotopic effects in pure and γ-irradiated triglycine selenate crystals were investigated using the specific heat (C p ) technique. The obtained results showed an interesting dependence of the critical behavior of C p on the deuterium content. With increasing content of deuterium, the character of the phase transition changed from a second order (λ-type) to a first order transition. After γ-irradiation, the behavior of C p around the phase transition region was essentially affected. The transition temperature, T c , decreased and ΔC p depressed, and the transition became broad. It was noted that the effect of γ-irradiation is opposite to the isotopic effect. (author)

Thermometric titration of a free acid and of uranyl in spent fuel element solutions

International Nuclear Information System (INIS)

Zamek, M.; Strafelda, F.

1975-01-01

A method was elaborated of determining nitric acid in the presence of uranyl nitrate in both aqueous and non-aqueous solutions using a pyridine aqueous solution as a titration agent, and of determining excess uranyl after a hydrogen peroxide addition by a further titration using the same agent. Even a hundred-fold excess of magnesium did not disturb the titration. The method is used in operating solution analyses in the extraction fuel reprocessing in the presence of a small amount of plutonium and of fission products. The reproducibility and accuracy of the method varied in the order of tens to units per cent depending on the concentration of components to be determined. The procedure is applicable for test volumes ranging between 0.1 and 10 ml in concentrations of 1 to 10 -3 M. (author)

Interfacial Interaction of Titania Nanoparticles and Ligated Uranyl Species: A Relativistic DFT Investigation.

Science.gov (United States)

Zhao, Hong-Bo; Zheng, Ming; Schreckenbach, Georg; Pan, Qing-Jiang

2017-03-06

To understand interfacial behavior of actinides adsorbed onto mineral surfaces and unravel their structure-property relationship, the structures, electronic properties, and energetics of various ligated uranyl species adsorbed onto TiO 2 surface nanoparticle clusters (SNCs) were examined using relativistic density functional theory. Rutile (110) and anatase (101) titania surfaces, experimentally known to be stable, were fully optimized. For the former, models studied include clean and water-free Ti 27 O 64 H 20 (dry), partially hydrated (Ti 27 O 64 H 20 )(H 2 O) 8 (sol) and proton-saturated [(Ti 27 O 64 H 20 )(H 2 O) 8 (H) 2 ] 2+ (sat), while defect-free and defected anatase SNCs involving more than 38 TiO 2 units were considered. The aquouranyl sorption onto rutile SNCs is energetically preferred, with interaction energies of -8.54, -10.36, and -2.39 eV, respectively. Energy decomposition demonstrates that the sorption is dominated by orbital attractive interactions and modified by steric effects. Greater hydrogen-bonding involvement leads to increased orbital interactions (i.e., more negative energy) from dry to sol/sat complexes, while much larger steric interaction in the sat complex significantly reduces the sorption interaction (i.e., more positive energy). For dry SNC, adsorbates were varied from aquo to aquo-carbonato, to carbonato, to hydroxo uranyl species. Longer U-O surf /U-Ti distances and more positive sorption energies were calculated upon introducing carbonato and hydroxo ligands, indicative of weaker uranyl sorption onto the substrate. This is consistent with experimental observations that the uranyl sorption rate decreases upon raising solution pH value or adding carbon dioxide. Anatase SNCs adsorbing aquouranyl are even more exothermic, because more bonds are formed than in the case of rutile. Moreover, the anatase sorption can be tuned by surface defects as well as its Ti and O stoichiometry. All the aquouranyl-SNC complexes show similar

Uranium (VI) chemistry at the interface solution/minerals (quartz and aluminium hydroxide): experiments and spectroscopic investigations of the uranyl surface species; Chimie de l'uranium (VI) a l'interface solution/mineraux (quartz et hydroxyde d'aluminium): experiences et caracterisations spectroscopiques

Energy Technology Data Exchange (ETDEWEB)

Froideval, A.

2004-09-15

This study deals with the understanding of the uranyl chemistry at the 0.1 M NaNO{sub 3} solution/mineral (quartz and aluminium hydroxide) interface. The aims are:(i) to identify and to characterize the different uranyl surface species (mononuclear, polynuclear complexes and/or precipitates...), i.e. the coordination environments of sorbed/precipitated uranyl ions, by using X-ray photoelectron spectroscopy (XPS), extended X-ray absorption fine structure (EXAFS) and time-resolved laser-induced fluorescence spectroscopy (TRLFS), and;(ii) to investigate the influence of pH, initial uranyl aqueous concentration and hydroxyl ligand concentration on the uranyl surface speciation. Our study on the speciation of uranyl ions at the quartz surface (i) confirms the formation of uranyl polynuclear/oligomers on quartz from moderate (1 {mu}mol/m{sup 2}) to high (26 {mu}mol/m{sup 2}) uranyl surface concentrations and (ii) show that theses polynuclear species coexist with uranyl mononuclear surface species over a pH range {approx_equal} 5-8.5 and a wide range of initial uranyl concentration o f the solutions (10-100 {mu}M). The uranyl concentration of these surface species depends on pH and on the initial uranyl aqueous concentration. Hydrate (surface-) precipitates and/or adsorbed polynuclear species and monomeric uranyl surface complexes are formed on aluminium hydroxide. Uranyl mononuclear complexes are predominant at acidic pH, as well as uranyl in solution or on the surface. Besides mononuclear species, precipitates and/or adsorbed polynuclear species are predominantly formed at neutral pH values on aluminium hydroxide. A main contribution of our investigations is that precipitation and/or adsorption of polynuclear species seem to occur at low uranyl surface concentrations (0.01-0.4 {mu}mol/m{sup 2}). The uranyl surface speciation is mainly dependent on the pH and the aluminol ligand concentration. (author)

An optional focusing SELENE extension to conventional neutron guides: A case study for the ESS instrument BIFROST

Energy Technology Data Exchange (ETDEWEB)

Hansen, U.B., E-mail: uhansen@nbi.ku.dk [Niels Bohr Institute, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen (Denmark); Bertelsen, M. [Niels Bohr Institute, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen (Denmark); Stahn, J. [Laboratory for Neutron Scattering and Imaging, Paul Scherrer Institut, CH-5232 Villigen PSI (Switzerland); Lefmann, K. [Niels Bohr Institute, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen (Denmark)

2017-04-21

The high brilliance at the European Spallation Source (ESS) will allow for performing experiments with much smaller samples than at present neutron facilities and in much more complex sample environments. However the higher flux also results in higher background from unwanted neutrons not originating from scattering of the sample. We here present a new design idea for beam delivery, where a 165 m ballistic guide system with good transport properties is followed by a 4–8 m SELENE guide system similar to Montel optics used for X-ray optics. We have investigated the system by detailed Monte-Carlo simulations using McStas. We show that under certain conditions, this set-up works surprisingly well, with a brilliance transfer of 20–60% for neutrons of wavelength 4 Å and above. We demonstrate that the guide system is able to focus the beam almost perfectly onto samples sizes in the range of 0.1–2 mm. We furthermore show that our SELENE system is insensitive to gravity and to realistic values of guide waviness. We argue that this guide system can be useful as an optional guide insert when small samples are used in the vicinity of bulky sample environment, e.g. for high-field or high-pressure experiments.

Subtle interactions and electron transfer between UIII, NpIII, or PuIII and uranyl mediated by the oxo group

International Nuclear Information System (INIS)

Arnold, Polly L.; Zegke, Markus; Hollis, Emmalina; Pecharman, Anne-Frederique; Love, Jason B.; Dutkiewicz, Michal S.; Walter, Olaf; Apostolidis, Christos; Magnani, Nicola; Griveau, Jean-Christophe; Colineau, Eric; Caciuffo, Roberto; Zhang, Xiaobin; Schreckenbach, Georg

2016-01-01

A dramatic difference in the ability of the reducing An III center in AnCp 3 (An=U, Np, Pu; Cp=C 5 H 5 ) to oxo-bind and reduce the uranyl(VI) dication in the complex [(UO 2 )(THF)(H 2 L)] (L=''Pacman'' Schiff-base polypyrrolic macrocycle), is found and explained. These are the first selective functionalizations of the uranyl oxo by another actinide cation. At-first contradictory electronic structural data are explained by combining theory and experiment. Complete one-electron transfer from Cp 3 U forms the U IV -uranyl(V) compound that behaves as a U V -localized single molecule magnet below 4 K. The extent of reduction by the Cp 3 Np group upon oxo-coordination is much less, with a Np III -uranyl(VI) dative bond assigned. Solution NMR and NIR spectroscopy suggest Np IV U V but single-crystal X-ray diffraction and SQUID magnetometry suggest a Np III -U VI assignment. DFT-calculated Hirshfeld charge and spin density analyses suggest half an electron has transferred, and these explain the strongly shifted NMR spectra by spin density contributions at the hydrogen nuclei. The Pu III -U VI interaction is too weak to be observed in THF solvent, in agreement with calculated predictions. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Mechanistic study of the interaction of uranyl ions with zirconium oxide and zirconium silicate; Etude mecanistique de l'interaction des ions uranyle avec l'oxyde et le silicate de zirconium

Energy Technology Data Exchange (ETDEWEB)

Lomenech, C

2002-04-01

This work deals with structural and thermodynamic studies of the sorption of uranyl species on zircon and zirconia. After determination of the specific areas, of the pH of the isoelectric points, and of the sorption site numbers, thermodynamic data were obtained using alpha spectrometry, for different uranyl concentrations, different background electrolytes (NaClO{sub 4} or KNO{sub 3}) and different ionic strengths. The structural identification of the surface complexes and sorption sites was carried out using several spectroscopies: XPS spectroscopy allowed a determination of the nature of the sorption sites ({identical_to}Zr-O- on zirconia and {identical_to}Si-O- on zircon). Whereas fluorescence decay measurements gave the number of surface species, the combined use of XPS spectroscopy and laser spectro-fluorimetry enabled us to correlate differences in bonding energies and emission wavelengths with differences in the nature of the background electrolyte or in the pH of sorption; DRIFT spectroscopy was a powerful tool for the determination of the presence of sorbed uranyl nitrate species. EXAFS results clearly showed a splitting of the equatorial oxygen atoms in two shells, corresponding to a polydentate, inner-sphere complex. EXAFS results also indicated strong similarities between dry samples and in situ experiments, which confirms the validity of all the spectroscopic measurements. Macroscopic thermodynamic data were then modeled using a surface complexation model (2 pK and constant capacitance models), the results of the structural study being used as constraints for the simulation code FITEQL. (author)

Uranyl ion complexation by the tripodal ligand nitrilo-tri-acetate

Energy Technology Data Exchange (ETDEWEB)

Thuery, P. [CEA Saclay, DSM/DRECAM/SCM, F-91191 Gif Sur Yvette, (France)

2007-07-01

Reaction of uranyl nitrate with N-(2-acetamido)iminodiacetic acid (ADA) under hydrothermal conditions resulted in the hydrolysis of the amide group and the isolation of the complex [(UO{sub 2})(HNTA)(H{sub 2}O){sub 2}], in which each nitrilo-tri-acetate ligand, protonated at the N site, bridges three metal atoms to give rise to infinite ladder-like ribbons built from 2:2 metallacycles. (author)

Investigation of Uranyl Nitrate Ion Pairs Complexed with Amide Ligands using Electrospray Ionization Ion Trap Mass Spectrometry and Density Functional Theory

International Nuclear Information System (INIS)

Groenewold, Gary S.; Dinescu, Adriana; Benson, Michael T.; Gresham, Garold L.; van Stipdonk, Michael J.

2011-01-01

Ion populations formed from electrospray of uranyl nitrate solutions containing different amides vary depending on ligand nucleophilicity and steric crowding at the metal center. The most abundant species were ion pair complexes having the general formula (UO2(NO3)(amide)n=2,3)+, and complexes containing the amide conjugate base, reduced uranyl UO2+, and a 2+ charge were also formed. The formamide experiment produced the greatest diversity of species that stems from weaker amide binding leading to dissociation and subsequent solvent coordination or metal reduction. Experiments using methyl formamide, dimethyl formamide, acetamide, and methyl acetamide produced ion pair and doubly charged complexes that were more abundant, and less abundant complexes containing solvent or reduced uranyl. This pattern is reversed in the dimethylacetamide experiment, which displayed reduced doubly charged complexes and augmented reduced uranyl complexes. DFT investigations of the tris-amide ion pair complexes showed that inter-ligand repulsion distorts the amide ligands out of the uranyl equatorial plane, and that complex stabilities do not increase with increasing amide nucleophilicity. Elimination of an amide ligand largely relieves the interligand repulsion, and the remaining amide ligands become closely aligned with the equatorial plane in the structures of the bis-amide ligands. The studies show that the phenomenological distribution of coordination complexes in a metal-ligand electrospray experiment is a function of both ligand nucleophilicity and interligand repulsion, and that the latter factor begins exerting influence even in the case of relatively small ligands like the substituted methyl-formamide and methyl-acetamide ligands.

Beryllium(II), manganese(II) and uranyl(VI)-salicylamide complexes

Energy Technology Data Exchange (ETDEWEB)

Maurya, P L; Agarwala, B V; Dey, A K [Allahabad Univ. (India)

1977-01-01

The preparation, composition, general properties and i.r. absorption spectra of the solid chelates formed by salicylamide with beryllium(II), manganese(II) and uranyl(VI) are described. The complexes have been synthesized by refluxing a mixture of ethanolic solutions of the reactants (metal:ligand :: 1:2) for several hours in the presence of alkali. Attempts to isolate the complexes by the interaction of ethanolic solutions of the metal salts and the ligand in the absence of alkali did not succeed.

Structural and lithological conditioning of the large karst systems of the Sierra de los Organos, Pinar del Rio, Cuba; Condicionantes estructurales y litologicas de los grandes sistemas karsticos de la Sierra de los Organos, Pinar del Rio, Cuba

Energy Technology Data Exchange (ETDEWEB)

Diaz Guanche, C.; Ramirez Hernandez, R.; Farfan Gonzalez, H.; Estevez Cruz, E.; Ordaz Hernandez, A.; Aldana Vilas, C.

2016-07-01

he karst, a complex phenomenon, is governed by a number of variables which dictate its genesis and evolution. Among these variables tectonic settings and lithology play the main role. In Cuba, approximately 65% of the territory is occupied by karst. The Sierra de los Organos, part of Cordillera de Guaniguanico, has some of the largest karstic systems in the country. With the aim of demonstrating the relationship between the spatial and morphological development of the underground karstic systems and the geological structure and lithology of the area, several structural and morphological measurements and field observations have been made. These measurements and observations allowing us to conclude that the karstic processes take place mainly in massive, relatively homogeneous and very thick limestone in the Sierra de los Organos. Moreover, these rocks are characterized by both low porosity and a high degree of fracturing. These karstic forms are also conditioned by the existence of various fracturing systems with general NE-SW and NW-SE orientations. Interception of these fracturing systems provides, as expected, areas with the largest volumes of karstic cavities. (Author)

Complexation of uranyl ion with sulfonates. One- to three-dimensional assemblies with 1,5- and 2,7-naphthalenedisulfonates

Energy Technology Data Exchange (ETDEWEB)

Thuery, Pierre [NIMBE, CEA, CNRS, Universite Paris-Saclay, CEA Saclay, Gif-sur-Yvette (France); Harrowfield, Jack [ISIS, Universite de Strasbourg (France)

2017-02-03

Uranyl nitrate was treated with the sodium salt of either 1,5- or 2,7-naphthalenedisulfonate (1,5-ndsNa{sub 2} or 2,7-ndsNa{sub 2}, respectively) under (solvo)-hydrothermal conditions, in the presence of additional coligands and/or metal cations, to give six new complexes, which were characterized by determination of their crystal structures. Complex [UO{sub 2}(1,5-nds)(H{sub 2}O)] (1) crystallizes as a three-dimensional (3D) framework, with both sulfonate groups coordinated in the O,O{sup '}-bridging mode. In the presence of the N-chelating species 2,2{sup '}-bipyridine (bipy) or 1,10-phenanthroline (phen), the three complexes [(UO{sub 2}){sub 2}(1,5-nds)(OH){sub 2}(bipy){sub 2}].H{sub 2}O (2), [(UO{sub 2}){sub 2}(1,5-nds)(OH){sub 2}(bipy){sub 2}].bipy (3) and [(UO{sub 2}){sub 2}(1,5-nds)(OH){sub 2}(phen){sub 2}] (4) were obtained, in which doubly hydroxide-bridged uranyl dimers are assembled into one-dimensional (1D) chains by bis(unidentate) disulfonate ligands. Complex [Cu(bipy){sub 2}Cl][UO{sub 2}(2,7-nds)(OH)].H{sub 2}O (5) displays anionic, two-dimensional (2D) sheets in which unidentate/O,O{sup '}-bridging disulfonate ligands link hydroxide-bridged uranyl dimers. In the additional presence of cucurbit[6]uril (CB6), complex [(UO{sub 2}){sub 4}Na{sub 4}(2,7-nds){sub 2}(CB6)Cl{sub 4}O{sub 2}(H{sub 2}O){sub 10}].5H{sub 2}O (6) crystallizes as a 3D framework of intricate architecture, with bis(μ{sub 3}-oxo)-bridged uranyl tetranuclear moieties connected to CB6-bound sodium cations by doubly O,O{sup '}-bridging disulfonates. Complexes 2 and 4 display intense and well-resolved uranyl emission in the solid state, while nearly complete quenching is observed in 3 and 5. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Crystal structure of the (REE)–uranyl carbonate mineral shabaite-(Nd)

Czech Academy of Sciences Publication Activity Database

Plášil, Jakub; Škoda, R.

2017-01-01

Roč. 62, č. 2 (2017), s. 97-105 ISSN 1802-6222 R&D Projects: GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : shabaite-(Nd) * uranyl carbonate * rare-earth elements * crystal structure * mineral evolution Subject RIV: DB - Geology ; Mineralogy OBOR OECD: Geology Impact factor: 0.609, year: 2016

Recuperation of uranyl ions from effluents by means of microbiological collectors

International Nuclear Information System (INIS)

Cecal, A.; Palamaru, I.; Humelnicu, D.; Goanta, M.; Rudic, V.; Salaru, V.V.; Gulea, A.

1997-01-01

This paper deals with the study of bioaccumulation of uranyl ions (UO 2 2+ ) from industrial effluents, using microbiological collectors: Nostoc linkia sp., Tolipotrix sp., Spirulina sp., Porphyridium cruentum and also the glucide extract of P. cruentum. The values of retaining degree of UO 2 2+ on the biomass, for several experimental conditions, were established between 14.22 and 91.99%

Complexes of uranyl with N-oxides of heterocyclic amines. Electron-vibrational absorption spectra

International Nuclear Information System (INIS)

Jezowska-Trzebiatowska, B.; Wieczorek, M.

1977-01-01

A number of coordination compounds formed by uranyl chloride and nitrate with N-oxides of heterocyclic amines have been prepared and characterized by spectral measurements in the absorption region 20000-50000 cm -1 . The electrons and vibronic transitions have been determined and discussed. (author)

Modulation of the unpaired spin localization in Pentavalent Uranyl Complexes

Energy Technology Data Exchange (ETDEWEB)

Vetere, V.; Maldivi, P.; Mazzanti, M. [CEA Grenoble, INAC, SCIB, laboratoire de reconnaissance ionique et chimie de coordination, 38 (France); Vetere, V. [UMR5626, laboratoire de chimie et physique quantique, universite de Toulouse, 31 - Toulouse (France)

2010-06-15

The electronic structure of various complexes of pentavalent uranyl species, namely UO{sub 2}{sup +}, is described, using DFT methods, with the aim of understanding how the structure of the ligands may influence the localisation of the unpaired 5f electron of uranium (V) and, finally, the stability of such complexes towards oxidation. Six complexes have been inspected: [UO{sub 2}py{sub 5}]{sup +} (1), [(UO{sub 2}py{sub 5})KI{sub 2}] (2), [UO{sub 2}(salan-{sup t}Bu{sub 2})(py)K] (3), [UO{sub 2}(salophen-{sup t}Bu{sub 2})(thf)K] (4), [UO{sub 2}(salen-{sup t}Bu{sub 2})(py)K] (5), [and UO{sub 2}-cyclo[6]pyrrole]{sup 1-} (6), chosen to explore various ligands. In the five first complexes, the UO{sub 2}{sup +} species is well identified with the unpaired electron localized on the 5f uranium orbital. Additionally, for the salan, salen and salophen ligands, some covalent interactions have been observed, resulting from the presence of both donor and acceptor binding sites. In contrast, the last complex is best described by a UO{sub 2}{sup 2+} uranyl (VI) coordinated by the anionic radical cyclo-pyrrole, the highly delocalized p orbitals set stabilizing the radical behaviour of this ligand. (authors)

Mechanistic study of the interaction of uranyl ions with zirconium oxide and zirconium silicate

International Nuclear Information System (INIS)

Lomenech, C.

2002-04-01

This work deals with structural and thermodynamic studies of the sorption of uranyl species on zircon and zirconia. After determination of the specific areas, of the pH of the isoelectric points, and of the sorption site numbers, thermodynamic data were obtained using alpha spectrometry, for different uranyl concentrations, different background electrolytes (NaClO 4 or KNO 3 ) and different ionic strengths. The structural identification of the surface complexes and sorption sites was carried out using several spectroscopies: XPS spectroscopy allowed a determination of the nature of the sorption sites (≡Zr-O- on zirconia and ≡Si-O- on zircon). Whereas fluorescence decay measurements gave the number of surface species, the combined use of XPS spectroscopy and laser spectro-fluorimetry enabled us to correlate differences in bonding energies and emission wavelengths with differences in the nature of the background electrolyte or in the pH of sorption; DRIFT spectroscopy was a powerful tool for the determination of the presence of sorbed uranyl nitrate species. EXAFS results clearly showed a splitting of the equatorial oxygen atoms in two shells, corresponding to a polydentate, inner-sphere complex. EXAFS results also indicated strong similarities between dry samples and in situ experiments, which confirms the validity of all the spectroscopic measurements. Macroscopic thermodynamic data were then modeled using a surface complexation model (2 pK and constant capacitance models), the results of the structural study being used as constraints for the simulation code FITEQL. (author)

Selenium deficiency occurs in some patients with moderate-to-severe cirrhosis and can be corrected by administration of selenate but not selenomethionine: a randomized controlled trial123

Science.gov (United States)

Burk, Raymond F; Hill, Kristina E; Motley, Amy K; Byrne, Daniel W; Norsworthy, Brooke K

2015-01-01

Background: Selenomethionine, which is the principal dietary form of selenium, is metabolized by the liver to selenide, which is the form of the element required for the synthesis of selenoproteins. The liver synthesizes selenium-rich selenoprotein P (SEPP1) and secretes it into the plasma to supply extrahepatic tissues with selenium. Objectives: We conducted a randomized controlled trial to determine whether cirrhosis is associated with functional selenium deficiency (the lack of selenium for the process of selenoprotein synthesis even though selenium intake is not limited) and, if it is, whether the deficiency is associated with impairment of selenomethionine metabolism. Design: Patients with Child-Pugh (C-P) classes A, B, and C (mild, moderate, and severe, respectively) cirrhosis were supplemented with a placebo or supranutritional amounts of selenium as selenate (200 or 400 μg/d) or as selenomethionine (200 μg/d) for 4 wk. Plasma SEPP1 concentration and glutathione peroxidase (GPX) activity, the latter due largely to the selenoprotein GPX3 secreted by the kidneys, were measured before and after supplementation. Results: GPX activity was increased more by both doses of selenate than by the placebo in C-P class B patients. The activity was not increased more by selenomethionine supplementation than by the placebo in C-P class B patients. Plasma selenium was increased more by 400 μg Se as selenate than by the placebo in C-P class C patients. Within the groups who responded to selenate, there was a considerable variation in responses. Conclusion: These results indicate that severe cirrhosis causes mild functional selenium deficiency in some patients that is associated with impaired metabolism of selenomethionine. This trial was registered at clinicaltrials.gov as NCT00271245. PMID:26468123

Sorption of radioiodine in organo-clays and -soils

Energy Technology Data Exchange (ETDEWEB)

Bors, J. (Niedersaechsisches Inst. fuer Radiooekologie, Hannover (Germany, F.R.))

1990-01-01

In the framework of investigations on the sorption of radioiodine to natural and artificially altered soil components, a number of clay minerals and natural soils were treated with quaternary alkylammonium ions to replace the exchangeable metal cations. With help of batch experiments the resulting organo-clays were tested with respect to their sorption capability of radioiodine quantified by the distribution ratio (R{sub D}-value). Treatment of bentonite, vermiculite and cretaceous clay as well as of samples from natural horizons of chernozem soil with hexadecylpyridinium (HDPY{sup +}) and benzethonium (BE{sup +}) exhibited sorptions rates and amounts, which are several orders of magnitude higher than those of the respective untreated samples. Moderate increases of the R{sub D}-values were found after cation exchange with hexadecyltrimethylammonium (HDTMA{sup +}), while the applications of trimethylphenylammonium (TMPA{sup +}) and tetramethylammonium (TMA{sup +}) were ineffective. Considerable sorption of radioiodine was observed with the commercially available Bentone. (orig.).

Synthesis and X-ray diffraction study of new uranyl malonate and oxalate complexes with carbamide

International Nuclear Information System (INIS)

Medvedkov, Ya. A.; Serezhkina, L. B.; Grigor’ev, M. S.; Serezhkin, V. N.

2016-01-01

Two new malonate-containing uranyl complexes with carbamide of the formulas [UO 2 (C 3 H 2 O 4 )(Urea) 2 ] (I) and [UO 2 (C 3 H 2 O 4 )(Urea) 3 ] (II), where Urea is carbamide, and one uranyl oxalate complex of the formula [UO 2 (C 2 O 4 )(Urea) 3 ] (III) were synthesized, and their crystals were studied by X-ray diffraction. The main structural units in crystals I are the electroneutral chains [UO 2 (C 3 H 2 O 4 )(Urea) 2 ] ∞ belonging to the crystal-chemical group AT 11 M 2 1 (A = UO 2 2+ , T 11 = C 3 H 2 O 4 2- , M 1 = Urea) of uranyl complexes. Crystals II and III are composed of the molecular complexes [UO 2 (L)(Urea) 3 ], where L = C 3 H 2 O 4 2- or C 2 O 4 2- , belonging to the crystal-chemical group AB 01 M 3 1 (A = UO 2 2+ , B 01 = C 3 H 2 O 4 2- or C 2 O 4 2- , M 1 = Urea). The characteristic features of the packing of the uranium-containing complexes are discussed in terms of molecular Voronoi–Dirichlet polyhedra. The effect of the Urea: U ratio on the structure of uranium-containing structural units is considered.

Fixation and reduction of uranium by natural organic matter: reaction mechanisms and kinetics

International Nuclear Information System (INIS)

Nakashima, S.; Perruchot, A.; Trichet, J.; Disnar, J.R.

1987-01-01

The reactivity of lignite towards soluble uranyl species in an aqueous medium is experimentally investigated as a function of temperature (between 20 0 C and 400 0 C). The fixation process starts near 45 0 C, with reduction beginning around 120 0 C. The fixation process leads to the formation of chemically and thermally stable organo-uranyl species. The reduction of free uranyl species is accompanied by a stoichiometric (2:1) liberation of protons into the medium. These protons originate from the organic matter which thus undergoes dehydrogenation. The general evolution of the carbonaceous residue in the course of this reaction shows that alcoholic and aliphatic hydrocarbon groups are responsible for the reduction. This chemical dehydrogenation could explain the low hydrogen content of natural organic materials associated with uraniferous deposits. The kinetics of the reduction step have been studied at 180 0 C, 190 0 C and 200 0 C. The kinetic parameters determined over this temperature range, and the extrapolation made to 20 0 C, show that reduction can be a crucial process in the geochemical behaviour of uranium especially in the thermal conditions in which sedimentary basins evolve [fr

Uranyl determination using pyridylazoresorcinol as complexing active by adsorb voltametry technique with cathodic redissolution

International Nuclear Information System (INIS)

Ohara, A.K.; Farias, P.A.M.

1990-01-01

The development method for uranyl ion determination by the optimization of chemical reaction and instrumental parameters is shown. This method is based on preconcentration stage, where in adsorptive accumulation of metallic complex in a static electrode is presented. (author)

Preparation and Characterization of Cu(In,GaSe2 Thin Films by Selenization of Cu0.8Ga0.2 and In2Se3 Precursor Films

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Jiang Liu

2012-01-01

Full Text Available Se-containing precursor films with two different compositions were prepared by magnetron sputtering from and targets, and then were selenized using Se vapor. The effects of precursor composition and selenization temperature on the film properties were investigated. The results show that Se phase plays a critical role in film growth and electrical properties of CIGS films. The Cu-rich films exhibit different surface morphology and better crystallinity, as compared to the Cu-poor films. All the CIGS films exhibit p-type conductivity. The resistivity of the Cu-rich films is about three orders of magnitude lower than that of the Cu-poor films, which is attributed to the presence of p-type highly conductive Se phase.

Effect of diluent on extraction of uranyl nitrate from nitric acid solution by tri-n-octylamine

International Nuclear Information System (INIS)

Kojima, Takashi; Ukon, Toshiaki; Fukutomi, Hiroshi

1979-01-01

The distribution ratios in the extraction equilibriums of uranylnitrate from 3 M HNO 3 by tri-n-octylamine (TOA) nitrate salt in nitrobenzene, chlorobenzene, benzene, toluene, cyclohexane, nitrobenzene-benzene and benzene-cylohexane mixtures have been determined in varying the concentrations of uranyl nitrate and TOA nitrate salt. The extraction mechanisms have been discussed in detail based on the law of mass action. It has been concluded that the extractions of uranyl nitrate by TOA nitrate salt in nitrobenzene, 74% nitrobenzene-benzene and 49% nitrobenzene-benzene mixture are represented by the equation TOAHNO 3 (org) + UO 2 2+ (aq) + 2 NO 3 - (aq) = TOAHUO 2 (NO 3 - ) 3 (org), while the extractions of uranyl nitrate by TOA nitrate salt in chlorobenzene, benzene, toluene, cyclohexane, benzene-cyclohexane mixtures and 24% nitrobenzene-benzene mixture are represented by the equation 2 TOAHNO 3 (org) + UO 2 2+ (aq) + 2 NO 3 - (aq) = TOAHUO 2 (NO 3 ) 3 TOAHNO 3 (org). In the latter the extraction equilibrium constants increase in the order of chlorobenzene < benzene < toluene < cyclohexane and with decreasing of the volume fraction of benzene in benzene-cyclohexane mixtures. The effects of diluent have been discussed in detail on the basis of the Hildebrand-Scatchard theory of regular solutions. (author)

Efficient tetracycline adsorption and photocatalytic degradation of rhodamine B by uranyl coordination polymer

Science.gov (United States)

Ren, Ya-Nan; Xu, Wei; Zhou, Lin-Xia; Zheng, Yue-Qing

2017-07-01

Two mixed uranyl-cadmium malonate coordination polymers [(UO2)2Cd(H-bipy)2(mal)4(H2O)2]·4H2O 1 and [(UO2)Cd(bipy)(mal)2]·H2O 2 (H2mal = malonic acid, bipy =4,4‧-bipyridine) have been synthesized in room temperature. Compound 1 represents a one-dimensional (1D) chain assembly of Cd(II) ions, uranyl centers and malonate ligands. Compound 2 exhibits a two-dimensional (2D) 2D +2D → 3D polycatenated framework based on inclined interlocked 2D 44 sql grids. The two compounds have been characterized by elemental analysis, IR and UV-vis spectroscopy, thermal analysis, powder X-ray diffraction and photoluminescence spectroscopy. And the ferroelectric property of 2 also has been studied. Moreover, compound 2 exhibits good photocatalytic activity for dye degradation under UV light and is excellent adsorbent for removing tetracycline antibiotics in the aqueous solution.

Uranyl-organic assemblies with the macrocyclic ligand 1, 4, 8, 11-tetra-aza-cyclo-tetradecane-1, 4, 8, 11-tetraacetate (TETA)

International Nuclear Information System (INIS)

Thuery, Pierre

2010-01-01

Three uranyl ion complexes obtained from the reaction of uranyl nitrate hexahydrate and 1, 4, 8, 11-tetra-aza-cyclo-tetradecane-1, 4, 8, 11-tetraacetic acid (H 4 TETA) were characterized by their crystal structure. The centrosymmetric macrocycle, in the [3434] conformation with either carbon or nitrogen atoms as corners, is zwitterionic, with four carboxylate groups and two or four protonated nitrogen atoms. The complexes [(UO 2 ) 2 (H 2 TETA)(C 2 O 4 )(H 2 O) 2 ] (1) and [UO 2 (H 4 TETA)(H 2 O)].NO 3 .Cl (2) were synthesized under hydrothermal conditions and 1 includes additional oxalate ligands generated in situ. Both compounds are two-dimensional polymers in which the four-fold monodentate macrocyclic ligand unites either four uranyl oxalate dinuclear species (1) or isolated uranyl ions (2). Complex 3, [UO 2 (H 2 TETA)(H 2 O)].6H 2 O, was obtained at room temperature and, although it displays the same stoichiometry as 2, it differs from it by being a three-dimensional framework. Both 2 and 3 present channels containing either counter-ions or water molecules. As often observed, the water content of the low-temperature species, 3, is higher than that of the high-temperature one, 2. (author)

Gamma-radiation and isotopic effect on the critical behavior in triglycine selenate crystals

Energy Technology Data Exchange (ETDEWEB)

Kassem, M.E.; Hamed, A.E.; Abulnasr, L.; Abboudy, S. [Alexandria Univ. (Egypt). Dept. of Physics

1994-11-01

Isotopic effects in pure and {gamma}-irradiated triglycine selenate crystals were investigated using the specific heat (C{sub p}) technique. The obtained results showed an interesting dependence of the critical behavior of C{sub p} on the deuterium content. With increasing content of deuterium, the character of the phase transition changed from a second order ({lambda}-type) to a first order transition. After {gamma}-irradiation, the behavior of C{sub p} around the phase transition region was essentially affected. The transition temperature, T{sub c}, decreased and {Delta}C{sub p} depressed, and the transition became broad. It was noted that the effect of {gamma}-irradiation is opposite to the isotopic effect. (author).

Study of the Cupriavidus metallidurans CH34 resistance of selenite and selenate oxy-anions: accumulation, localisation and transformation of selenium; Etude de la resistance de Cupriavidus metallidurans CH34 aux oxyanions selenite et seleniate: accumulation, localisation et transformation du selenium

Energy Technology Data Exchange (ETDEWEB)

Avoscan, L

2007-06-15

Selenium is an essential trace element for the living organisms but it is very toxic at high concentration. Selenite and selenate oxides, soluble forms, highly toxic and bio-assimilable, are the most prevalent forms in the environment. Some soil micro-organisms play a dominant role and contribute to the natural cycle of selenium. Our study model, Cupriavidus (formerly Ralstonia) metallidurans CH34, a telluric bacterium characteristic of metal-contaminated biotopes, is known to resist selenite by reducing it into elemental selenium, an insoluble and less toxic form of selenium. In order to better understand the mechanisms of selenium reduction in the bacteria, three methods of speciation were combined (XAS (XANES and EXAFS), HPLC-ICP-MS and SDS-PAGEPIXE). They were completed by the direct quantification of selenium accumulated in the bacteria. Speciation analyses highlighted the existence of two mechanisms of reduction of selenium oxides in C. metallidurans CH34. Assimilation transforms selenite and selenate into organic selenium, identified as seleno-methionine and leads to its non-specific incorporation into bacterial proteins (presence of selenious proteins). Detoxication precipitates selenite in nano-particles of elemental selenium. This way of detoxication is not set up after an exposure to selenate although it is nevertheless possible to detect elemental selenium but in very small amount compared to the exposure of selenite. Seleno-diglutathion is detected in bacteria stressed by an exposure to selenate in medium limited in sulphate. Bacteria exposed to selenite accumulate 25 times more selenium than when they are exposed to selenate. The study of mutants resistant to selenite, which do not express the membrane protein DedA, showed that the accumulation of selenium after exposure to selenite is decreased compared with the wild strain meaning probable link between the transport of selenite and the DedA protein. Finally, selenate would use the sulphate permease

Obtention of Uo3 by means of denitration of uranyl nitrate in a fluidized-bed

International Nuclear Information System (INIS)

Santos, W.R. dos; Costa, P.A.

1990-01-01

A fluidized-bed pilot unit for the production of UO 3 installed at IPEN-CNEN/SP is described. Its capacity is of 20 kg U/h in a continuous process. The main components of this pilot unit are: a system for the concentration of nuclearly pure uranyl nitrate (≅ 100 g U/L), a system for the denitration of the concentrated uranyl nitrate, an absorption system for NO 2 produced during the denitration reaction and, finally, a system for the dissolution of UO 3 that does not meet the specifications. The operational troubles found during the initial runs are presented. The results of the physical and chemical analysis of the UO 3 produced are discussed and a comparison is made for the UO 3 obtained by both fluidized-bed and wet processes. (author) [pt

An evaluation of Tiron (sodium 4,5-dihydroxybenzene-1,3-disulfonate) as a rescue agent for the nephropathy induced by uranyl fluoride (UO2F2) in rats

International Nuclear Information System (INIS)

Zalups, R.K.

1991-01-01

Tiron (sodium 4,5-dihydroxybenzene-1,3-disulfonate) was tested as a potential rescue agent for the nephropathy induced by uranyl fluoride (UO2F2) in rats. When uranyl fluoride was administered (i.v.) to male Sprague-Dawley rats at a dose that delivered 250 micrograms U/kg, moderate to severe cellular necrosis occurred in pars recta segments of proximal tubules in the cortex and outer stripe of the outer medulla of the rats' kidneys within four days after treatment. The severity of renal tubular injury was not significantly diminished when rats were given a 10, 100 or 1,000 mg/kg dose of Tiron (i.p.) 30 minutes after the administration of uranyl fluoride. No obvious protection was noted even when the rats were given a 1,000 mg/kg dose of Tiron 15, 30 and 90 minutes after the administration of uranyl fluoride. Therefore, Tiron does not appear to provide rats substantial protection against a dose of uranyl fluoride that induces moderate to severe renal injury

Computer simulation of uranyl uptake by the rough lipopolysaccharide membrane of Pseudomonas aeruginosa.

Science.gov (United States)

Lins, Roberto D; Vorpagel, Erich R; Guglielmi, Matteo; Straatsma, T P

2008-01-01

Heavy metal environmental contaminants cannot be destroyed but require containment, preferably in concentrated form, in a solid or immobile form for recycling or final disposal. Microorganisms are able to take up and deposit high levels of contaminant metals, including radioactive metals such as uranium and plutonium, into their cell wall. Consequently, these microbial systems are of great interest as the basis for potential environmental bioremediation technologies. The outer membranes of Gram-negative microbes are highly nonsymmetric and exhibit a significant electrostatic potential gradient across the membrane. This gradient has a significant effect on the uptake and transport of charged and dipolar compounds. However, the effectiveness of microbial systems for environmental remediation will depend strongly on specific properties that determine the uptake of targeted contaminants by a particular cell wall. To aid in the design of microbial remediation technologies, knowledge of the factors that determine the affinity of a particular bacterial outer membrane for the most common ionic species found in contaminated soils and groundwater is of great importance. Using our previously developed model for the lipopolysaccharide (LPS) membrane of Pseudomonas aeruginosa, this work presents the potentials of mean force as the estimate of the free energy profile for uptake of sodium, calcium, chloride, uranyl ions, and a water molecule by the bacterial LPS membrane. A compatible classical parameter set for uranyl has been developed and validated. Results show that the uptake of uranyl is energetically a favorable process relative to the other ions studied. At neutral pH, this nuclide is shown to be retained on the surface of the LPS membrane through chelation with the carboxyl and hydroxyl groups located in the outer core.

The Impact of Organo-Mineral Complexation on Mineral Weathering in the Soil Zone under Unsaturated Conditions

Science.gov (United States)

Michael, H. A.; Tan, F.; Yoo, K.; Imhoff, P. T.

2017-12-01

While organo-mineral complexes can protect organic matter (OM) from biodegradation, their impact on soil mineral weathering is not clear. Previous bench-scale experiments that focused on specific OM and minerals showed that the adsorption of OM to mineral surfaces accelerates the dissolution of some minerals. However, the impact of natural organo-mineral complexes on mineral dissolution under unsaturated conditions is not well known. In this study, soil samples prepared from an undisturbed forest site were used to determine mineral weathering rates under differing conditions of OM sorption to minerals. Two types of soil samples were generated: 1) soil with OM (C horizon soil from 84-100cm depth), and 2) soil without OM (the same soil as in 1) but with OM removed by heating to 350°for 24 h). Soil samples were column-packed and subjected to intermittent infiltration and drainage to mimic natural rainfall events. Each soil sample type was run in duplicate. The unsaturated condition was created by applying gas pressure to the column, and the unsaturated chemical weathering rates during each cycle were calculated from the effluent concentrations. During a single cycle, when applying the same gas pressure, soils with OM retained more moisture than OM-removed media, indicating increased water retention capacity under the impact of OM. This is consistent with the water retention data measured by evaporation experiments (HYPROP) and the dew point method (WP4C Potential Meter). Correspondingly, silicon (Si) denudation rates indicated that dissolution of silicate minerals was 2-4 times higher in OM soils, suggesting that organo-mineral complexes accelerate mineral dissolution under unsaturated conditions. When combining data from all cycles, the results showed that Si denudation rates were positively related to soil water content: denundation rate increased with increasing water content. Therefore, natural mineral chemical weathering under unsaturated conditions, while

Tritium gettering from air with hydrogen uranyl phosphate. Revision 1

International Nuclear Information System (INIS)

Souers, P.C.; Uribe, F.S.; Stevens, C.G.; Tsugawa, R.T.

1985-01-01

Hydrogen uranyl phosphate (HUP), a solid proton electrolyte, getters tritium gas and water vapor from air by DC electrical action. We have reduced the formation of residual tritiated water to less than 2%, and demonstrated that HUP can clean a 5.5 m 3 working glove box. Data are presented to illustrate the parameters of the gettering and a model is derived. Two other tritium gettering electrolytes have been discovered. 9 refs., 5 figs., 3 tabs

Uranyl(VI)-acetylacetonate coordination compounds with various N-heterocyclic ligands

International Nuclear Information System (INIS)

Kawasaki, Takeshi; Nishimura, Tatsuru; Kitazawa, Takafumi

2010-01-01

Seven uranyl(VI) complexes, [UO 2 (acac) 2 (L)] [L=4-methylpyridine (1), 4-ethylpyridine (2), 2,4-dimethylpyridine (3), (-)-nicotine (4), and imidazole (5)], [{UO 2 (acac) 2 } 2 -(4,4'-bipyridine)] (6), and [(2,2'-bipyridine) 2 H][UO 2 (acac)(NO 3 ) 2 ] (7) have been synthesized and characterized crystallographically. The coordination geometry of U has a UNO 6 pentagonal-bipyramidal coordination in 1-6, and a UO 8 hexagonal-bipyramidal coordination in 7. (author)

Tris-amidoximate uranyl complexes via η2 binding mode coordinated in aqueous solution shown by X-ray absorption spectroscopy and density functional theory methods.

Science.gov (United States)

Zhang, Linjuan; Qie, Meiying; Su, Jing; Zhang, Shuo; Zhou, Jing; Li, Jiong; Wang, Yu; Yang, Shitong; Wang, Shuao; Li, Jingye; Wu, Guozhong; Wang, Jian Qiang

2018-03-01

The present study sheds some light on the long-standing debate concerning the coordination properties between uranyl ions and the amidoxime ligand, which is a key ingredient for achieving efficient extraction of uranium. Using X-ray absorption fine structure combined with theoretical simulation methods, the binding mode and bonding nature of a uranyl-amidoxime complex in aqueous solution were determined for the first time. The results show that in a highly concentrated amidoxime solution the preferred binding mode between UO 2 2+ and the amidoxime ligand is η 2 coordination with tris-amidoximate species. In such a uranyl-amidoximate complex with η 2 binding motif, strong covalent interaction and orbital hybridization between U 5f/6d and (N, O) 2p should be responsible for the excellent binding ability of the amidoximate ligand to uranyl. The study was performed directly in aqueous solution to avoid the possible binding mode differences caused by crystallization of a single-crystal sample. This work also is an example of the simultaneous study of local structure and electronic structure in solution systems using combined diagnostic tools.

THE EFFECTS OF SODIUM SELENITE AND SELENIZED YEAST SUPPLEMENTATION INTO DIET FOR LAYING HENS ON SELECTED QUALITATIVE PARAMETERS OF TABLE EGGS

Directory of Open Access Journals (Sweden)

HENRIETA ARPÁŠOVÁ

2009-10-01

Full Text Available In this experiment the effects of supplementation of the diet for laying hens with sodium selenite (SS or selenized yeast (SY on whole egg and egg shell quality of layers were studied. The chickens of Shaver Starcross 288 strain were randomly divided at the day of hatching into 4 groups (n=12; in each. The birds were fed from Day 1 of life to 9 months of age with diets differing in amounts and/or forms of selenium. Control group received basal diet (BD containing selenium naturally occurring in feeds (0.1 mg Se/kg of dry matter (DM. First and second experimental group of chickens were fed with a same BD enriched with equivalent dose of Se 0.4 mg/kg DM in form of sodium selenite or selenized yeast, respectively. The feed for third experimental group of birds consisted of BD supplemented with selenized yeast to the final amount of selenium 1.0 mg/kg DM. The egg weight was significantly higher in the groups with SY supplementation only. On the contrary the egg shell ratio was significantly lower in the groups with SY supplementation in both amounts. The width of egg was significantly increased in the groups with selenium supplementation in both forms. The value of egg shell strength was significantly decreased in group with SY in the highest amount 0.9 mg/kg DM The average egg shell thickness was the highest in the experimental group with Se-yeast in amount 0.9 mg/kg DM, however different was not significant compared with control group. The results showed that the most of selected parameters of egg quality appeared to be significantly influenced by selenium supplementation into laying hen’s basal diet.

Determination of uranyl nitrate diffusion coefficients in organic and aqueous media using the porous diaphragm method

International Nuclear Information System (INIS)

Chierice, G.O.

1974-01-01

The diffusion coefficient is one of the parameters necessary for the obtention of the extraction exponential coefficients, that are contained within the H.T.U. (height of transfer unity) calculation expression, when operating with continuous organic phase. The organic phase used was tri-n-butyl-phosphate (TBP) and varsol in the 35% and 65% proportions respectively. After each experiment, the uranium content present in each compartment was spectrophotometrically determined and the quantities contained in the aqueous phases were determined by means of volumetric titration. It was found out that the uranyl ion diffusion coefficient is two and one half times less in organic phase, this just being attributed to the greater interactions of the uranyl ions in organic than in aqueous medium

Uptake and distribution of organo-iodine in deep-sea corals.

Science.gov (United States)

Prouty, Nancy G; Roark, E Brendan; Mohon, Leslye M; Chang, Ching-Chih

2018-07-01

Understanding iodine concentration, transport, and bioavailability is essential in evaluating iodine's impact to the environment and its effectiveness as an environmental biogeotracer. While iodine and its radionuclides have proven to be important tracers in geologic and biologic studies, little is known about transport of this element to the deep sea and subsequent uptake in deep-sea coral habitats. Results presented here on deep-sea black coral iodine speciation and iodine isotope variability provides key information on iodine behavior in natural and anthropogenic environments, and its geochemical pathway in the Gulf of Mexico. Organo-iodine is the dominant iodine species in the black corals, demonstrating that binding of iodine to organic matter plays an important role in the transport and transfer of iodine to the deep-sea corals. The identification of growth bands captured in high-resolution scanning electron images (SEM) with synchronous peaks in iodine variability suggest that riverine delivery of terrestrial-derived organo-iodine is the most plausible explanation to account for annual periodicity in the deep-sea coral geochemistry. Whereas previous studies have suggested the presence of annual growth rings in deep-sea corals, this present study provides a mechanism to explain the formation of annual growth bands. Furthermore, deep-sea coral ages based on iodine peak counts agree well with those ages derived from radiocarbon ( 14 C) measurements. These results hold promise for developing chronologies independent of 14 C dating, which is an essential component in constraining reservoir ages and using radiocarbon as a tracer of ocean circulation. Furthermore, the presence of enriched 129 I/ 127 I ratios during the most recent period of skeleton growth is linked to nuclear weapons testing during the 1960s. The sensitivity of the coral skeleton to record changes in surface water 129 I composition provides further evidence that iodine composition and isotope

Uptake and distribution of organo-iodine in deep-sea corals

Science.gov (United States)

Prouty, Nancy G.; Roark, E. Brendan; Mohon, Leslye M.; Chang, Ching-Chih

2018-01-01

Understanding iodine concentration, transport, and bioavailability is essential in evaluating iodine's impact to the environment and its effectiveness as an environmental biogeotracer. While iodine and its radionuclides have proven to be important tracers in geologic and biologic studies, little is known about transport of this element to the deep sea and subsequent uptake in deep-sea coral habitats. Results presented here on deep-sea black coral iodine speciation and iodine isotope variability provides key information on iodine behavior in natural and anthropogenic environments, and its geochemical pathway in the Gulf of Mexico. Organo-iodine is the dominant iodine species in the black corals, demonstrating that binding of iodine to organic matter plays an important role in the transport and transfer of iodine to the deep-sea corals. The identification of growth bands captured in high-resolution scanning electron images (SEM) with synchronous peaks in iodine variability suggest that riverine delivery of terrestrial-derived organo-iodine is the most plausible explanation to account for annual periodicity in the deep-sea coral geochemistry. Whereas previous studies have suggested the presence of annual growth rings in deep-sea corals, this present study provides a mechanism to explain the formation of annual growth bands. Furthermore, deep-sea coral ages based on iodine peak counts agree well with those ages derived from radiocarbon (14C) measurements. These results hold promise for developing chronologies independent of 14C dating, which is an essential component in constraining reservoir ages and using radiocarbon as a tracer of ocean circulation. Furthermore, the presence of enriched 129I/127I ratios during the most recent period of skeleton growth is linked to nuclear weapons testing during the 1960s. The sensitivity of the coral skeleton to record changes in surface water 129I composition provides further evidence that iodine composition and isotope

Synthesis of Cu/TiO{sub 2}/organo-attapulgite fiber nanocomposite and its photocatalytic activity for degradation of acetone in air

Energy Technology Data Exchange (ETDEWEB)

Zhang, Gaoke, E-mail: gkzhang@whut.edu.cn; Wang, He; Guo, Sheng; Wang, Junting; Liu, Jin

2016-01-30

Graphical abstract: - Highlights: • A novel Cu/TiO{sub 2}/organo-attapulgite fiber nanocomposite was synthesized successfully. • Micro-mesopore nanocomposite structure was in favor of the degradation of acetone. • CTAB modification improved the adsorption capability of the catalyst. • The photocatalytic degradation mechanism of the acetone by the catalyst was studied. - Abstract: The Cu/TiO{sub 2}/organo-attapulgite fiber (CTOA) nanocomposite was synthesized by a facile method and was used for photocatalytic degradation of acetone in air under UV light irradiation. The as-prepared samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscope (SEM), transmission electron microscopy (TEM), UV–vis diffuse reflectance spectrum (UV–vis DRS), inductively coupled plasma (ICP) spectrometry and N{sub 2} adsorption–desorption measurement. The results showed that the structure of organo-attapulgite (OAT) had no obvious change as compared to unmodified attapulgite (AT) and the attapulgite fibers in the OAT were well-dispersed. Both micropores and mesopores exist in the CTOA catalyst. The CTOA catalysts prepared at the Cu/TiO{sub 2} molar ratio of 0.003 shows an excellent photocatalytic activity for the degradation of acetone in air. The synergistic effect of Cu species and cetyltrimethylammonium bromide modification can be responsible for the enhanced photocatalytic activity of the CTOA catalyst. The mechanism of the photocatalytic degradation of acetone by the CTOA catalyst was discussed.

The effect of organo-clay on the dielectric properties of silicone rubber

International Nuclear Information System (INIS)

Razzaghi-Kashani, M; Gharavi, N; Javadi, S

2008-01-01

Dielectric elastomers are highly deformable and fast response smart materials capable of actuation under electric fields. Among commercially available dielectric elastomers, silicone rubber can be compounded with different fillers in order to modify its electrical and mechanical properties. To study the effect of organically modified montmorillonite (OMMT) on the dielectric properties of silicone rubber, OMMT was added to this rubber at two levels, 2% and 5%, using two methods, low-shear and high-shear mixing. Composites were characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The XRD patterns showed different crystallite structures for silicate platelets in the rubber matrix as a result of the two different mixing methods. In low-shear mixing, the ordered crystallite structure of the clay remains almost unchanged, whereas in high-shear mixing it loses its ordered structure, leading to the disappearance of the diffraction peaks. SEM and AFM micrographs depicted better dispersion and more uniform distribution of the organo-clay under high-shear mixing compared to those obtained by low-shear mixing. The tensile properties also confirmed the different degree of dispersion of the nano-clay resulting from the two different methods of mixing. The dielectric properties of the composites were measured under AC electric fields, and the results were compared with reference silicone rubbers with no OMMT. It was shown that the order of organo-clay layers in the less dispersed structure of the clay imparts an additional ionic polarization and higher dielectric permittivity compared to the case where the clay layers are more dispersed and lost their order. The storage and loss dielectric constants of base silicone rubber increase when it is compounded with OMMT

Contribution to the study of the mechanism of extraction of uranyl chloride by long chain aliphatic amines; Contribution a l'etude du mecanisme d'extraction du chlorure d'uranyle par les amines aliphatiques a longues chaines

Energy Technology Data Exchange (ETDEWEB)

Rubinstein, G R [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1965-06-01

After having studied and developed the mechanisms which may 'a priori' explain the extraction process (co-ordination, ion association or intermediate mechanism), experience shows that ion association only should be taken into consideration. The structure of the organic complex of uranyl chloride has been defined on the basis of the study of the variation of the distribution coefficient of uranium between the two phases at the equilibrium as a function of successively the activity of Cl{sup -} ions in the aqueous phase, the concentration of amine salt in the organic phase and finally of the concentration of uranium in the aqueous phase. The plotting of the results in bi-logarithmic co-ordinates enables us to propose the following formula for the extracted compound: UO{sub 2}Cl{sub 4}{sup --}(NR{sub 3}H{sup +}){sub 2}. The calculation of the equilibrium constant of formation of the organic compound of uranyl chloride has been possible in the case of diluted solutions of uranium only. (author) [French] Apres avoir expose et developpe les mecanismes qui a priori pouvaient expliquer le processus d'extraction (coordination, association d'ions ou mecanisme intermediaire), le recours a l'experience a finalement permis de ne retenir que l'association d'ions. La structure du complexe organique de chlorure d'uranyle a ete definie a partir de l'etude de la variation du coefficient de partage de l'uranium entre les deux phases a l'equilibre en fonction successivement de l'activite des ions Cl{sup -} en phase aqueuse, de la concentration de sel d'amine en phase organique et enfin de la concentration d'uranium de la phase aqueuse. La representation bilogarithmique des resultats de ces essais a permis de proposer la formule suivante pour le compose extrait: UO{sub 2}Cl{sub 4}{sup --}(NR{sub 3}H{sup +}){sub 2}. Le calcul de la constante d'equilibre de formation du compose organique de chlorure d'uranyle a ete seulement possible pour les solutions diluees en uranium. (auteur)

Determination of halogens, silicon, phosphorus, carbon, sulfur, tributyl phosphate and of free acid in uranyl nitrate solutions

International Nuclear Information System (INIS)

Chu Van Vinh

2003-01-01

High-purity uranium compounds are widely used in nuclear field in the form of uranyl nitrate or uranium oxides. In production of uranium material the estimation and the control of products quality is necessary and very important. Halogens was separated from uranium compounds by steam distillation and they were later determined by high performance liquid chromatography (HPLC) for Cl - , Br - , I - ions. Br - was also determined by spectrophotometric and iodide by the individual pulse polarography. Silicon and phosphorus in uranyl nitrate solutions were determined by the photometric method. Sulfur was determined as sulfate form by the measurement of turbidity by the titrimetry. TBP in kerosene and free acid in aqueous solution were determined by the titration. (author)

Complex formation between uranyl and various thiosemicarbazide derivatives

International Nuclear Information System (INIS)

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

1987-01-01

Complex formation between hexavalent uranium and salicylaldehyde thiosemicarbazone (H 2 L), salicylaldehyde S-methyl-isothiosemicarbazone (H 2 Q), S-methyl-N 1 ,N 4 -bis(salicylidene)isothiosemicarbazide(H 2 Z), and thiosemicarbazidodiacetic acid (H 2 R) has been studied spectrophotometrically in solution. Stability constants for complexes having the composition UO 2 A have been calculated. Solid uranyl derivatives having the composition UO 2 L x 2H 2 O, UO 2 Q x 2H 2 O, UO 2 Z x 2H 2 O, and UO 2 R x 2H 2 O have been obtained. These derivatives were isolated and their IR spectroscopic behavior and thermal properties were investigated

Complexing in the system Rb2SeO4-UO2SeO4-H2O

International Nuclear Information System (INIS)

Kuchumova, N.V.; Shtokova, I.P.; Serezhkina, L.B.; Serezhkin, V.N.

1989-01-01

Method of isothermal solubility at 25 deg C is used to study interaction of rubidium and uranyl selenates in aqueous solution. Formation of congruently soluble Rb 2 UO 2 (SeO 4 ) 2 x2H 2 O and Rb 2 (UO 2 ) 2 x(SeO 4 ) 3 x6H 2 O is stated. For the last compound crystallographic characteristics (a=10.668; b=14.935(9); c=13.891(7) A; β=104.94(1); Z=4, sp.gr. P2 1 /c) are determined. Thermal decomposition of a compound results in formation of Rb 2 U 2 O 7

Probing the influence of N-donor capping ligands on supramolecular assembly in molecular uranyl materials

Energy Technology Data Exchange (ETDEWEB)

Carter, Korey P.; Kalaj, Mark; Cahill, Christopher L. [Department of Chemistry, The George Washington University, Washington, DC (United States)

2016-01-15

The syntheses and crystal structures of six new compounds containing the UO{sub 2}{sup 2+} cation, 3,5-dichlorobenzoic acid, and a chelating N-donor [2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (dimethylphen), 2,2{sup '}:6{sup '},2''-terpyridine (terpy), 4{sup '}-chloro-2,2{sup '}:6{sup '},2''-terpyridine (Cl-terpy), or 2,4,6-tris(2-pyridyl)-s-triazine (TPTZ)] are reported. Single-crystal X-ray diffraction analysis of these materials enabled the exploration of the structural relationship between the benzoic acids and the chelating N-donor as well as providing a platform to evaluate the effects of ligand choice on uranyl hydrolysis and subsequent oligomerization. At an unadjusted pH (ca. 3), a mix of uranyl monomers and dimers are observed, dimer formation resulting from both bridging carboxylate linkers and hydroxo bridges. Assembly by halogen- and hydrogen-bonding interactions as well as π-π interactions was observed depending on the experimental conditions utilized. Further, spectroscopic characterization (both vibrational and luminescence) of complexes 1, 4, and 5 to explore the effects of the electron-donating ability of the capping ligand on the corresponding uranyl luminescence and vibrational spectra suggests that there is a relationship between the observed bathochromic shifts and the electron-donating ability of the capping ligands. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Probing the influence of N-donor capping ligands on supramolecular assembly in molecular uranyl materials

International Nuclear Information System (INIS)

Carter, Korey P.; Kalaj, Mark; Cahill, Christopher L.

2016-01-01

The syntheses and crystal structures of six new compounds containing the UO 2 2+ cation, 3,5-dichlorobenzoic acid, and a chelating N-donor [2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (dimethylphen), 2,2 ' :6 ' ,2''-terpyridine (terpy), 4 ' -chloro-2,2 ' :6 ' ,2''-terpyridine (Cl-terpy), or 2,4,6-tris(2-pyridyl)-s-triazine (TPTZ)] are reported. Single-crystal X-ray diffraction analysis of these materials enabled the exploration of the structural relationship between the benzoic acids and the chelating N-donor as well as providing a platform to evaluate the effects of ligand choice on uranyl hydrolysis and subsequent oligomerization. At an unadjusted pH (ca. 3), a mix of uranyl monomers and dimers are observed, dimer formation resulting from both bridging carboxylate linkers and hydroxo bridges. Assembly by halogen- and hydrogen-bonding interactions as well as π-π interactions was observed depending on the experimental conditions utilized. Further, spectroscopic characterization (both vibrational and luminescence) of complexes 1, 4, and 5 to explore the effects of the electron-donating ability of the capping ligand on the corresponding uranyl luminescence and vibrational spectra suggests that there is a relationship between the observed bathochromic shifts and the electron-donating ability of the capping ligands. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Glutathione attenuates uranyl toxicity in Lactococcus lactis

International Nuclear Information System (INIS)

Fahmy, Karim; Oertel, Jana; Solioz, M.

2017-01-01

We investigated the role of intracellular glutathione (GSH), which in a large number of taxa plays a role in the protection against the toxicity of heavy metals. Anaerobically grown Lactococcus lactis containing an inducible GSH synthesis pathway was used as a model organism allowing the study of GSH-dependent uranyl detoxification without interference from additional reactive oxygen species. Microcalorimetric measurements of the metabolic heat showed that intracellular GSH attenuates the toxicity of uranium at a concentration in the range of 10-150 μM. Isothermal titration calorimetry revealed the endothermic binding of U(VI) to the carboxyl group(s) of GSH. The data indicate that the primary detoxifying mechanism is the intracellular sequestration of carboxyl-coordinated U(VI) into an insoluble complex with GSH.

Glutathione attenuates uranyl toxicity in Lactococcus lactis

Energy Technology Data Exchange (ETDEWEB)

Fahmy, Karim; Oertel, Jana [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biophysics; Obeid, M. [Technische Univ. Dresden (Germany); Solioz, M. [Bern Univ. (Switzerland)

2017-06-01

We investigated the role of intracellular glutathione (GSH), which in a large number of taxa plays a role in the protection against the toxicity of heavy metals. Anaerobically grown Lactococcus lactis containing an inducible GSH synthesis pathway was used as a model organism allowing the study of GSH-dependent uranyl detoxification without interference from additional reactive oxygen species. Microcalorimetric measurements of the metabolic heat showed that intracellular GSH attenuates the toxicity of uranium at a concentration in the range of 10-150 μM. Isothermal titration calorimetry revealed the endothermic binding of U(VI) to the carboxyl group(s) of GSH. The data indicate that the primary detoxifying mechanism is the intracellular sequestration of carboxyl-coordinated U(VI) into an insoluble complex with GSH.

Preparations and crystal structures of 8 coordinate uranyl(VI) complexes having macrocyclic ligands derived from pyrroledicarboxialdehydes and diamines

International Nuclear Information System (INIS)

Komagine, J.; Takeda, M.; Takahashi, M.

2006-01-01

Six 8-coordinate uranyl(VI) complexes with macrocyclic Schiff base ligands derived from 2,6-pyrroledicarboxialdehyde and diamines are prepared and the crystal structures for two of them are determined focusing on the relation between the size of the ligands and U-N bond distances. No difference in average uranyl bond distances and bond angles are observed between [UO 2 (bipytn)](a) and [UO 2 (bipydmtn)](b). U-N bonds of these complexes are, however, not equal; the U-N(pyrrole) bonds [2.45(a), 2.44(b) A] are much shorter than the U-N(imine) bonds [2.67(a), 2.67(b) A]. (author)

Selenized milk casein in the diet of BALB/c nude mice reduces growth of intramammary MCF-7 tumors

International Nuclear Information System (INIS)

Warrington, Jenny M; Kim, Julie JM; Stahel, Priska; Cieslar, Scott RL; Moorehead, Roger A; Coomber, Brenda L; Corredig, Milena; Cant, John P

2013-01-01

Dietary selenium has the potential to reduce growth of mammary tumors. Increasing the Se content of cows’ milk proteins is a potentially effective means to increase Se intake in humans. We investigate the effects of selenized milk protein on human mammary tumor progression in immunodeficient BALB/c nude mice. Four isonitrogenous diets with selenium levels of 0.16, 0.51, 0.85 and 1.15 ppm were formulated by mixing low- and high-selenium milk casein isolates with a rodent premix. MCF-7 cells were inoculated into the mammary fat pad of female BALB/c nude mice implanted with slow-release 17 β-estradiol pellets. Mice with palpable tumors were randomly assigned to one of the four diets for 10 weeks, during which time weekly tumor caliper measurements were conducted. Individual growth curves were fit with the Gompertz equation. Apoptotic cells and Bcl-2, Bax, and Cyclin D1 protein levels in tumors were determined. There was a linear decrease in mean tumor volume at 70 days with increasing Se intake (P < 0.05), where final tumor volume decreased 35% between 0.16 and 1.15 ppm Se. There was a linear decrease in mean predicted tumor volume at 56, 63 and 70 days, and the number of tumors with a final volume above 500 mm 3 , with increasing Se intake (P < 0.05). This tumor volume effect was associated with a decrease in the proportion of tumors with a maximum growth rate above 0.03 day -1 . The predicted maximum volume of tumors (V max ) and the number of tumors with a large V max , were not affected by Se-casein. Final tumor mass, Bcl-2, Bax, and Cyclin D1 protein levels in tumors were not significantly affected by Se-casein. There was a significantly higher number of apoptotic cells in high-Se tumors as compared to low-Se tumors. Taken together, these results suggest that turnover of cells in the tumor, but not its nutrient supply, were affected by dairy Se. We have shown that 1.1 ppm dietary Se from selenized casein can effectively reduce tumor progression in an MCF-7

Prioritization of the Oral (Ingestive) Hazard of Industrial Chemicals

Science.gov (United States)

2011-10-28

or Respiration - respiratory obstruction VCVN1* "Vrednie chemichescie veshestva. Neorganicheskie soedinenia elementov I-IV groopp" (Hazardous...section Lungs, Thorax, or Respiration - respiratory depression Gastrointestinal - changes in structure or function of esophagus MJAUAJ Medical Journal...impaired Nutritional and Gross Metabolic - metabolic alkalosis JTCTDW Journal of Toxicology, Clinical Toxicology. 33 Sodium chloride #(T3) 7647-14-5 LD50

New insight into the ternary complexes of uranyl carbonate in seawater.

Science.gov (United States)

Beccia, M R; Matara-Aho, M; Reeves, B; Roques, J; Solari, P L; Monfort, M; Moulin, C; Den Auwer, C

2017-11-01

Uranium is naturally present in seawater at trace levels and may in some cases be present at higher concentrations, due to anthropogenic nuclear activities. Understanding uranium speciation in seawater is thus essential for predicting and controlling its behavior in this specific environmental compartment and consequently, its possible impact on living organisms. The carbonato calcic complex Ca 2 UO 2 (CO 3 ) 3 was previously identified as the main uranium species in natural seawater, together with CaUO 2 (CO 3 ) 3 2- . In this work, we further investigate the role of the alkaline earth cation in the structure of the ternary uranyl-carbonate complexes. For this purpose, artificial seawater, free of Mg 2+ and Ca 2+ , using Sr 2+ as a spectroscopic probe was prepared. Combining TRLIF and EXAFS spectroscopy, together with DFT and theoretical thermodynamic calculations, evidence for the presence of Sr alkaline earth counter ion in the complex structure can be asserted. Furthermore, data suggest that when Ca 2+ is replaced by Sr 2+ , SrUO 2 (CO 3 ) 3 2- is the main complex in solution and it occurs with the presence of at least one monodentate carbonate in the uranyl coordination sphere. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sorption of uranyl species on zircon and zirconia

International Nuclear Information System (INIS)

Lomenech, C.; Drot, R.; Simoni, E.; Ehrhardt, J.J.; Mielczarski, J.

2002-01-01

The safety of a long-term storage of radioactive waste in deep geological repositories would be strongly affected by the migration properties of radionuclides through the different barriers to the surface of the earth. Since the main process involved in the retention of radioactive ions is their sorption at the water/ mineral interface, a quantitative description of the sorption reactions is needed. Macroscopic data have for a long time been the only source of information used to propose a modelling of sorption equilibria, although they bring no direct information on the nature of the sorbed species; a microscopic structural investigation of the surface complexes is difficult indeed, because of the small amount of matter sorbed. Thus, in this study, parallel to the macroscopic measurements, different complementary spectroscopic techniques have been used in order to determine the nature of the surface species. As the final purpose of such a study is the simulation of the experimental retention data, the precise structural identification of the sorption equilibria will then be very useful to constrain the data simulation code. In this work, we present the results of both macroscopic and microscopic studies of the sorption of uranyl species on zircon and zirconia. The first part of our macroscopic approach was the surface characterisation of the non-sorbed materials by the determination of the specific areas, of the pH of the isoelectric points, and of the sorption site numbers, while the second part aimed at obtaining the sorption isotherms (percentage of sorption versus pH), which was performed using alpha spectrometry, for different uranyl concentrations, media (NaClO 4 or KNO 3 ) and ionic strengths. The spectroscopic identification of the different surface complexes and sorption sites has been carried out using four different spectroscopies. Whereas tune-resolved laser spectro-fluorimetry gave a direct answer concerning the number of surface species (only for a

Structural variability in uranyl-lanthanide hetero-metallic complexes with DOTA and oxalato ligands

International Nuclear Information System (INIS)

Thuery, P.

2009-01-01

Four novel 4f-5f hetero-metallic complexes could be obtained from the reaction of uranyl and lanthanide nitrates with DOTA (H 4 L) under hydrothermal conditions. In all cases, as in the previous examples reported, additional oxalato ligands are formed in situ. Variations in the stoichiometry of the final products and the presence of hydroxo ions in some cases appear to result in a large structural variability. In the two isomorphous complexes [(UO 2 ) 2 Ln 2 (L) 2 (C 2 O 4 )] with Ln = Sm(1) or Eu(2), the lanthanide ion is located in the N 4 O 4 site and is also bound to a carboxylate oxygen atom from a neighbouring unit, to give zigzag chains which are further linked to one another by [(UO 2 ) 2 (C 2 O 4 )] 2+ di-cations, resulting in the formation of a 3D framework. In [(UO 2 ) 4 Gd 2 (L) 2 (C 2 O 4 ) 3 (H 2 O) 6 ].2H 2 O (3), 2D bilayer subunits of the 'double floor' type with uranyl oxalate pillars are assembled into a 3D framework by other, disordered uranyl ions. [(UO 2 ) 2 Gd(L)(C 2 O 4 )(OH)].H 2 O (4) is a 2D assembly in which cationic {[(UO 2 ) 2 (C 2 O 4 )(OH)] + } n chains are linked to one another by the [Gd(L)] - groups. The most notable feature of this compound is the environment of the 4f ion, which is eight-coordinate and twisted square anti-prismatic (TSA'), instead of nine-coordinate mono-capped square anti-prismatic (SA), as generally observed in DOTA complexes of gadolinium(III) and similarly-sized ions. (author)

Synthesis, structural investigation and kinetic studies of uranyl(VI) unsymmetrical Schiff base complexes

Czech Academy of Sciences Publication Activity Database

Asadi, Z.; Asadi, M.; Zeinali, A.; Ranjkeshshorkaei, M.; Fejfarová, Karla; Eigner, Václav; Dušek, Michal; Dehnokhalaji, A.

2014-01-01

Roč. 126, č. 6 (2014), s. 1673-1683 ISSN 0974-3626 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : uranyl schiff base complexes * kinetic study * kinetics of thermal decomposition * X-ray crystallography * cyclic voltammetry Subject RIV: CA - Inorganic Chemistry Impact factor: 1.191, year: 2014

Comparative studies on the corrosion protection effect of DBSA-doped polyaniline prepared from in situ emulsion polymerization in the presence of hydrophilic Na+-MMT and organophilic organo-MMT clay platelets

International Nuclear Information System (INIS)

Chang, K.-C.; Lai, M.-C.; Peng, C.-W.; Chen, Y.-T.; Yeh, J.-M.; Lin, C.-L.; Yang, J.-C.

2006-01-01

A series of polyaniline (PANI)/Na + -montmorillonite (MMT) clay and PANI/organo-MMT nanocomposite materials have been successfully prepared by in situ emulsion polymerization in the presence of inorganic nanolayers of hydrophilic Na + -MMT clay or organophilic organo-MMT clay with DBSA and KPS as surfactant and initiator, respectively. The as-synthesized Na + -PCN and organo-PCN materials were characterized and compared by Fourier transformation infrared (FTIR) spectroscopy, wide-angle powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). Na + -PCN materials in the form of coatings with low loading of Na + -MMT clay (e.g., 3 wt.%, CLAN3) on cold-rolled steel (CRS) were found much superior in corrosion protection over those of organo-PCN materials with same clay loading based on a series of electrochemical measurements of corrosion potential, polarization resistance, corrosion current and impedance spectroscopy in 5 wt.% aqueous NaCl electrolyte. The molecular weights of PANI extracted from PCN materials and neat PANI were determined by gel permeation chromatography (GPC) with NMP as eluant. Effects of material composition on the gas permeability, optical properties and electrical conductivity of neat PANI and a series of PCN materials, in the form of free-standing film, solution and powder-pressed pellet, were also studied by gas permeability analyzer (GPA), ultraviolet-vis spectra and four-point probe technique, respectively

Molecular dynamics simulation of local structure and vibrational spectrum of uranyl (UO2)2+ in vitreous B2O3

International Nuclear Information System (INIS)

Zhuang, Z.-H.; Liu, G. K.; Beitz, J. V.

2000-01-01

Laser spectroscopic and extended X-ray absorption fine structure (EXAFS) spectra have shown that uranium in B 2 O 3 glass matrix forms uranyl in the electronic configuration of (UO 2 ) 2+ ,but its surrounding structure is not well known. Understanding of uranyl local structure, ion-ligand interaction, and chemical stability on the nanometer scale in glasses is essential in management of long-term performance of high-level nuclear wastes after disposal in a geologic repository. In the present work, the structure, phonon density of states, and vibrational spectrum of vitreous B 2 O 3 and the surrounding environment that contains a uranyl ion have been studied using a molecular dynamics (MD) simulation method that utilizes the Born-Mayer-Huggins and Coulomb pair potentials and the Stillinger-Weber three-body potential. A system of 406 ions was considered in our calculation. Simulation of a thermal quenching from 3000 K to 300 K was performed to generate a uniform and equilibrium model glass matrix before structure configuration and vibrational frequencies were obtained from the system. The structure of the simulated glass is in agreement with that reported by Krogh-Moe and Mozzi et al. The characteristic network of planar boroxol (B 3 O 6 ) rings is evident in the simulated system. A configuration of a U 6+ cation in the vitreous B 2 O 3 matrix is shown in Fig. 1. It is shown that a nearly linear (UO 2 ) 2+ uranyl ion is coordinated by four equatorial oxygen anions in an approximately planar arrangement. The U-O bond length is approximately 0.178 nm for the axial oxygen and 0.254 nm for the equatorial oxygen, which is in good agreement with the U-O distances obtained from fitting EXAFS spectra. Based on the simulated model structure, the uranyl vibrational spectrum is simulated and compared with experimental results obtained using site-selective fluorescence line narrowing (FLN) techniques

New thermo-sensitive chelating surfactants for selective solvent-free extraction of uranyl nitrate

International Nuclear Information System (INIS)

Prevost, S.; Larpent, C.; Testard, F.; Coulombeau, H.; Baczko, K.; Berthon, L.; Desvaux, H.; Madic, C.; Zemb, T.

2004-01-01

Functional surfactants were synthesised by grafting a chelating group (amino-acid residue) to the tip of a poly-ethoxylated nonionic surfactant chain (C i E j : C i H 2i +1(OCH 2 CH 2 ) j OH)) or in a branched position. C i E j nonionic surfactants are known to be thermo-reversible and to exhibit a clouding phenomenon associated to phase separation of micelles. The functional surfactants retain both surface-active properties, characteristic thermo-reversible behaviour and have efficient complexing properties toward uranyl. In the presence of uranyl nitrate, small micelles are formed at ambient temperature and the de-mixing leads to a separation of the target ion trapped by the functional surfactant (cloud point extraction). Those surfactants are more efficient than mixture of classical C i E j and complexing agent solubilized in the micelles. This reveals a synergistic effect of the covalent bond between the chelating group and the nonionic surfactant C i E j . This paper presents a systematic study of the extraction and aggregation properties and the influence of the nature of the ions. (authors)

Controlled deprotection and reorganization of uranyl oxo groups in a binuclear macrocyclic environment

Energy Technology Data Exchange (ETDEWEB)

Jones, Guy M.; Arnold, Polly L.; Love, Jason B. [Edinburgh Univ. (United Kingdom). EaStCHEM School of Chemistry

2012-12-07

The silylated uranium(V) dioxo complex [(Me{sub 3}SiOUO){sub 2}(L){sub 2}] is inert to oxidation, but after two-electron reduction to [(Me{sub 3}SiOUO){sub 2}(L)]{sup 2-}, it can be desilylated to form [OU(μ-O){sub 2}UO(L){sub 2}]{sup 2-} with reinstated uranyl character. Removal of the silyl group uncovers new redox and oxo rearrangement chemistry for uranium, thus reforming the uranyl motif and involving the U{sup VI/V} couple in dioxygen reduction. [German] Der silylierte Dioxouran(V)-Komplex [(Me{sub 3}SiOUO){sub 2}(L){sub 2}] (A) ist inert gegen Oxidation, kann aber nach Zweielektronenreduktion zu [(Me{sub 3}SiOUO){sub 2}(L)]{sup 2-} (1) zu [OU(μ-O){sub 2}UO(L){sub 2}]{sup 2-} (2) mit wiederhergestelltem Uranylcharakter desilyliert werden. Beim Entfernen der Silylgruppe zeigt sich eine neue Redox- und Oxoumlagerungschemie des Urans unter Rueckbildung des Uranylmotivs sowie der Beteiligung des U{sup VI/V}-Paars an einer Disauerstoffreduktion.

Diluent and extractant effects on the enthalpy of extraction of uranium(VI) and americium(III) nitrates by trialkyl phosphates

International Nuclear Information System (INIS)

Srinivasan, T.G.; Vasudeva Rao, P.R.; Sood, D.D.

1998-01-01

The effect of various diluents such as n-hexane, n-heptane n-octane, isooctane, n-decane, n-undecane, n-dodecane, n-tetradecane, n-hexadecane, cyclohexane, benzene, toluene, p-xylene, mesitylene and o-dichlorobenzene on the enthalpy of extraction of uranyl nitrate by tri-n-amyl phosphate (TAP) over the temperature range 283 K--333 K has been studied. The results indicate that the enthalpy of extraction does not vary significantly with the diluents studied. Also enthalpies of extraction of uranyl nitrate and americium(III) nitrate by neutral organo phosphorous extractants such as tri-n-butyl phosphate (TBP), tri-n-amyl phosphate (TAP), tri-sec-butyl phosphate (TsBP), tri-isoamyl phosphate (TiAP) and tri-n-hexyl phosphate (THP) have been studied. An attempt has been made to explain the trends, on the basis of the nature of the solvate formed and the different terms which contribute to the overall enthalpy change

Crystal structure of the uranyl-oxide mineral rameauite

Energy Technology Data Exchange (ETDEWEB)

Plasil, Jakub [ASCR, Prague (Czech Republic). Inst. of Physics; Skoda, Radek [Masaryk Univ., Brno (Czech Republic). Dept. of Geological Sciences; Cejka, Jiri [National Museum, Prague (Czech Republic). Dept. of Mineralogy and Petrology; Bourgoin, Vincent; Boulliard, Jean-Claude [Pierre et Marie Curie Univ., Paris (France). Association Jean Wyart, Collection des Mineraux de Jussieu

2016-12-15

Rameauite is a rare supergene uranyl-oxide hydroxy-hydrate mineral that forms during hydration-oxidation weathering of uraninite. On the basis of single-crystal X-ray diffraction data collected on a microfocus source, rameauite is monoclinic, space group Cc, with a = 13.9458(19), b = 14.3105(19), c = 13.8959(18) Aa, β = 118.477(14) , V = 2437.7(6) Aa{sup 3} and Z = 4, with D{sub calc} = 5.467 g cm{sup -3}. The structure of rameauite (R = 0.060 for 1698 unique observed reflections) contains sheets of the β-U{sub 3}O{sub 8} topology, with both UO{sub 6} and UO{sub 7} bipyramids, which is similar to the sheets found in spriggite, ianthinite and wyartite. The sheets alternate with the interlayer, which contains K{sup +}, Ca{sup 2+} and H{sub 2}O molecules. Interstitial cations are linked into infinite chains that extend along [10-1]. Adjacent sheets are linked through K-O, Ca-O and H-bonds. The structural formula of rameauite is K{sub 2} Ca(H{sub 2}{sup [3]}O){sub 1}(H{sub 2}{sup [5]}O){sub 4}[(UO{sub 2}) {sub 6}O{sub 6}(OH){sub 4}](H{sub 2}{sup [4]}O){sub 1}. The empirical formula obtained from the average of eight electron-microprobe analyses is (on the basi s of 6 U p.f.u.) K{sub 1.87}(Ca{sub 1.10}Sr{sub 0.04}){sub Σ1.14}[(UO 2){sub 6}O{sub 6}(OH){sub 4.15}].6H{sub 2}O. The Raman spectrum is dominate d by U.O and O.H vibrations. A discussion of related uranyl-oxide minerals is given.

Influence of selenite and selenate supplementation on the chromium uptake and translocation in Allium cepa

International Nuclear Information System (INIS)

Karuna Shanker; Setia, Seema; Srivastava, Shalini; Dass, Sahab; Srivastava, Rohit; Satya Prakash; Srivastava, M.M.

1997-01-01

Pot experiments were conducted on onion plant to study the effects of selenite and selenate treatments (0.5-6.0) μg ml -1 on the uptake and translocation of root absorbed chromium irrigated with 2 and 5 μg ml -1 of chromium in sand and soil. Both the form of selenium (SeO 3 2- , and SeO 4 2- ) were found equally effective in reducing the chromium burden of the plant. No significant difference (p>0.05) in dry matter yields among various selenium treatments exist suggesting no salt injury occurred in the plants under prevailing conditions. (author). 10 refs., 1 tab

Cation-Cation Complexes of Pentavalent Uranyl: From Disproportionation Intermediates to Stable Clusters

Energy Technology Data Exchange (ETDEWEB)

Mougel, Victor; Horeglad, Pawel; Nocton, Gregory; Pecaut, Jacques; Mazzanti, Marinella [CEA, INAC, SCIB, Laboratoire de Reconnaissance Ionique et Chimie de Coordination, CEA-Grenoble, 38054 GRENOBLE, Cedex 09 (France)

2010-07-01

Three new cation cation complexes of pentavalent uranyl, stable with respect to the disproportionation reaction, have been prepared from the reaction of the precursor [(UO{sub 2}py{sub 5})-(KI{sub 2}py{sub 2})]{sub n} (1) with the Schiff base ligands salen{sup 2-}, acacen{sup 2-}, and salophen{sup 2-} (H{sub 2}salen N, N'-ethylene-bis(salicylidene-imine), H{sub 2}acacen=-N, N'-ethylenebis(acetylacetone-imine), H{sub 2}salophen=N, N'-phenylene-bis(salicylidene-imine)). The preparation of stable complexes requires a careful choice of counter ions and reaction conditions. Notably the reaction of 1 with salophen{sup 2-} in pyridine leads to immediate disproportionation, but in the presence of [18]crown-6 ([18]C-6) a stable complex forms. The solid-state structure of the four tetra-nuclear complexes ([UO{sub 2}-(acacen)]{sub 4}[{mu}{sub 8}-]{sub 2}[K([18]C-6)(py)]{sub 2}) (3) and ([UO{sub 2}(acacen)](4)[{mu}{sub 8}-]).2[K([222])(py)] (4) ([UO{sub 2}(salophen)](4)[{mu}{sub 8}-K]{sub 2}[mu(5)-KI]{sub 2}[(K([18]C-6)]).2 [K([18]C-6)-(thf){sub 2}].2I (5), and ([UO{sub 2}(salen)(4)][{mu}{sub 8}-Rb]{sub 2}[Rb([18]C-6)]{sub 2}) (9) ([222] = [222]cryptand, py =pyridine), presenting a T-shaped cation cation interaction has been determined by X-ray crystallographic studies. NMR spectroscopic and UV/Vis studies show that the tetra-nuclear structure is maintained in pyridine solution for the salen and acacen complexes. Stable mononuclear complexes of pentavalent uranyl are also obtained by reduction of the hexavalent uranyl Schiff base complexes with cobaltocene in pyridine in the absence of coordinating cations. The reactivity of the complex [U{sup V}O{sub 2}(salen)(py)][Cp*{sub 2}Co] with different alkali ions demonstrates the crucial effect of coordinating cations on the stability of cation cation complexes. The nature of the cation plays a key role in the preparation of stable cation cation complexes. Stable tetra-nuclear complexes form in the presence of K

Physico-chemical study of new functionalized surfactants having thermo sensitive de-mixing behaviour: use in extraction of uranyl nitrate

International Nuclear Information System (INIS)

Prevost, S.

2006-04-01

New thermo-sensitive functionalized surfactants with metal-chelating properties have been developed and their physical-chemistry studied. They associate a polyethoxylated nonionic surfactant (CiEj) block and a amino-acid residue as a chelating group. Functionalization preserves both properties of the thermo-sensitive surfactant moiety and the chelating group, a diamide closed to uranyl ionophore.The complexing group participates to the polar head group of the surfactant, increasing the area per molecule. As a result, functionalized surfactants form spherical micelles when diluted in water, and the concentrated part of their phase diagrams exhibits structures having higher curvatures than the nonionic precursor CiEj. The structure of the uranyl - diamide complex has been elucidated by NMR and ESI-MS and is of the type UO 2 (NO 3 ) 2 .L; the associated complexation constant, which is very low, has been evaluated by 1 H NMR.A nitrate salt, LiNO 3 , is added at high concentration to improve complexation. The effect of this salt has been analyzed, and was found to be rather similar to the effect on classical CiEj. When uranyl nitrate complexation occurs, the cloud point decreases dramatically, together with the reduction of the area per head group at micelle/solution interface. This effect can be minimized by using a nonionic precursor having a larger polar head group. The functionalized surfactants have been tested in the cloud point extraction of uranyl nitrate, and have proved their efficiency. Those results demonstrate the viability of the functionalized surfactants design, with a covalent link between a thermo-sensitive surfactant block and a chelating group. (author)

Application of the NICADonnan model for proton, copper and uranyl binding to humic acid

NARCIS (Netherlands)

Saito, T.; Nagasaki, S.; Tanaka, S.; Koopal, L.K.

2004-01-01

Humic acids are natural organic materials that play an important role in the migration of heavy metal and actinide ions in aquatic and soil systems. In the present study, the binding of protons, copper ions and uranyl ions to the purified Aldrich humic acid (PAHA) is investigated and the results are

Effect of selenization time on the structural and morphological properties of Cu(In,Ga)Se2 thin films absorber layers using two step growth process

Science.gov (United States)

Korir, Peter C.; Dejene, Francis B.

2018-04-01

In this work two step growth process was used to prepare Cu(In, Ga)Se2 thin film for solar cell applications. The first step involves deposition of Cu-In-Ga precursor films followed by the selenization process under vacuum using elemental selenium vapor to form Cu(In,Ga)Se2 film. The growth process was done at a fixed temperature of 515 °C for 45, 60 and 90 min to control film thickness and gallium incorporation into the absorber layer film. The X-ray diffraction (XRD) pattern confirms single-phase Cu(In,Ga)Se2 film for all the three samples and no secondary phases were observed. A shift in the diffraction peaks to higher 2θ (2 theta) values is observed for the thin films compared to that of pure CuInSe2. The surface morphology of the resulting film grown for 60 min was characterized by the presence of uniform large grain size particles, which are typical for device quality material. Photoluminescence spectra show the shifting of emission peaks to higher energies for longer duration of selenization attributed to the incorporation of more gallium into the CuInSe2 crystal structure. Electron probe microanalysis (EPMA) revealed a uniform distribution of the elements through the surface of the film. The elemental ratio of Cu/(In + Ga) and Se/Cu + In + Ga strongly depends on the selenization time. The Cu/In + Ga ratio for the 60 min film is 0.88 which is in the range of the values (0.75-0.98) for best solar cell device performances.

Identification of Uranyl Surface Complexes an Ferrihydrite: Advanced EXAFS Data Analysis and CD-MUSIC Modeling

NARCIS (Netherlands)

Rossberg, A.; Ulrich, K.U.; Weiss, S.; Tsushima, S.; Hiemstra, T.; Scheinost, A.C.

2009-01-01

Previous spectroscopic research suggested that uranium(VI) adsorption to iron oxides is dominated by ternary uranyl-carbonato surface complexes across an unexpectedly wide pH range. Formation of such complexes would have a significant impact on the sorption behavior and mobility of uranium in

A relativistic density functional study of uranyl hydrolysis and complexation by carboxylic acids in aqueous solution

International Nuclear Information System (INIS)

Ray, Rupashree Shyama

2009-01-01

In this work, the complexation of uranium in its most stable oxidation state VI in aqueous solution was studied computationally, within the framework of density functional (DF) theory. The thesis is divided into the following parts: Chapter 2 briefly summarizes the relevant general aspects of actinide chemistry and then focuses on actinide environmental chemistry. Experimental results on hydrolysis, actinide complexation by carboxylic acids, and humic substances are presented to establish a background for the subsequent discussion. Chapter 3 describes the computational method used in this work and the relevant features of the parallel quantum chemistry code PARAGAUSS employed. First, the most relevant basics of the applied density functional approach are presented focusing on relativistic effects. Then, the treatment of solvent effects, essential for an adequate modeling of actinide species in aqueous solution, will be introduced. At the end of this chapter, computational parameters and procedures will be summarized. Chapter 4 presents the computational results including a comparison to available experimental data. In the beginning, the mononuclear hydrolysis product of UO_2"2"+, [UO_2OH]"+, will be discussed. The second part deals with actinide complexation by carboxylate ligands. First of all the coordination number for uranylacetate will be discussed with respect to implications for the complexation of actinides by humic substances followed by the uranyl complexation of aromatic carboxylic acids in comparison to earlier results for aliphatic ones. In the end, the ternary uranyl-hydroxo-acetate are discussed, as models of uranyl humate complexation at ambient condition.

Selenization of mixed metal oxides for dense and ZnSe-free Cu{sub 2}ZnSnSe{sub 4} absorber films

Energy Technology Data Exchange (ETDEWEB)

Deng, Yitao; Chen, Guilin; Pan, Bin; Li, JianMin; Jiang, Guoshun; Liu, Weifeng, E-mail: liuwf@ustc.edu.cn; Zhu, Changfei, E-mail: cfzhu@ustc.edu.cn

2014-04-05

Highlights: • ZnSe-free CZTSe films with large grains was prepared from mixed oxides nanopraticles. • Appearance of Zn{sub 2}SnO{sub 4} in mixed oxides precursors leads to the absence of ZnSe secondary phrase. • To obtain pure CZTSe phase, different treating temperature was used. -- Abstract: Cu{sub 2}ZnSnSe{sub 4} (CZTSe) films were prepared by direct selenization of Cu{sub 2}O, SnO{sub 2} and Zn{sub 2}SnO{sub 4} precursors. Oxides precursors were prepared by baking hydroxides precipitation. In order to obtain ZnSe-free CZTSe films, Zn{sub 2}SnO{sub 4} was used to replace separated ZnO and SnO{sub 2} as one of the precursors. Through X-ray diffraction (XRD), scanning electron microscopy (SEM), it was found that CZTSe films, with micron-sized dense grains, were obtained in our work. From Raman spectra, it was also found that the ZnSe secondary phase was absent after the selenization. An energy bandgap about 0.86 eV was obtained in our work, which confirmed the Stannite-CZTSe structure.

Study of the transport characteristics of uranyl chloride in a highly concentrated aqueous solution of sodium chloride

International Nuclear Information System (INIS)

Murso, H.

1986-01-01

The purpose of this work was the study of the transport processes of uranyl chloride at various temperatures, in order to be able to estimate the danger potential of the intrusion of water during storage in salt form. For this the concentration dependency of the approximated principal diffusion coefficients of uranyl chloride in a table salt solution, which with a c(NaCl) = 5.2 mol/l is almost at the saturation point, was studied at 25, 40 and 50degC. The measurements were successful in the ternarian system UO 2 Cl 2 -NaCl-H 2 O with absorption optics. An unexpected temperature dependency of the diffusion coefficients was found, which reached its minimum at 40degC with UO 2 Cl 2 concentrations of less than 2x10 -2 mol/l. For comparison the diffusion coefficients were measured in the binary system UO 2 Cl 2 -H 2 O and compared with theoretical calculations. The cause for the poor correlation found here is thought to be the hydrolysis products, whose formation is strongly influenced by the foreign-electrolyte concentration (NaCl). For clarification, viscosity measurements and molar mass determinations (ultracentrifuge) will be done. Some pH-dependent hydrolysis equilibriums are being postulated and the equilibrium constants of uranyl hydroxo complexes are being determined by sedimentation analysis. (orig./RB) [de

Acute toxicity of uranium hexafluoride, uranyl fluoride and hydrogen fluoride

International Nuclear Information System (INIS)

Just, R.A.

1988-01-01

Uranium hexafluoride (UF 6 ) released into the atmosphere will react rapidly with moisture in the air to form the hydrolysis products uranyl fluoride (UO 2 F 2 ) and hydrogen fluoride (HF). Uranium compounds such as UF 6 and UO 2 F 2 exhibit both chemical toxicity and radiological effects, while HF exhibits only chemical toxicity. This paper describes the development of a methodology for assessing the human health consequences of a known acute exposure to a mixture of UF 6 , UO 2 F 2 , and HF. 4 refs., 2 figs., 5 tabs

Determination of the stability of the uranyl ion sipped in {tau}-hydrogen phosphate of zirconium in sodic form; Determinacion de la estabilidad del ion uranilo sorbido en {tau}-hidrogenofosfato de zirconio en forma sodica

Energy Technology Data Exchange (ETDEWEB)

Ordonez R, E.; Fernandez V, S.M. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico); Drot, R.; Simoni, E. [Universite de Paris-Sud-XI, Institut de Physique Nucleaire d' Orsay, Groupe de radiochimie, Bat. 100, 91406 Orsay (France)]. e-mail: edo@nuclear.inin.mx

2005-07-01

The stability of the uranyl sipped in the zirconium {tau}-hydrogen phosphate in sodic form ({tau}-NaZrP), was carried out characterizing the complexes formed by Laser spectroscopy in the visible region and by X-ray photoelectron spectroscopy. The material was prepared by a new synthesis technique working in nitrogen atmosphere and to low temperatures. The sorption of the uranyl ion was made in acid media with concentrations of 10{sup -4} and 10{sup -5} of uranyl nitrate and with ion forces of 0.1 and 0.5 M of NaClO{sub 4}. The spectra of induced fluorescence with laser (TRLFS) show that the uranyl is fixed in very acid media in three well differentiated species, to pH less acid, the specie of long half life disappears and are only those of short half life. The results of the binding energy obtained by XPS indicate that the binding energy of the uranyl confer it a stable character to the complex formed in the {tau}-NaZP, that makes to this material appropriate to retain to the uranyl in solution to high ion forces and in acid media. (Author)