A route to oligosaccharide-appended salicylaldehydes: useful building blocks for the synthesis of metal-salophen complexes.

PubMed

Bedini, Emiliano; Forte, Gianpiero; De Castro, Cristina; Parrilli, Michelangelo; Dalla Cort, Antonella

2013-08-16

A simple and general synthetic protocol to obtain oligosaccharide-appended salicylaldehydes, key intermediates for the synthesis of water-soluble metal-salophen complexes, is here reported. Six new aldehydes have been prepared and fully characterized as well as the corresponding zinc- and uranyl-salophen complexes. These new derivatives show very good solubility in water. Preliminary studies on the association of compound 19-U, that is, the uranyl maltotetraose derivative, with hydrogen phosphate and fluoride provide very encouraging results and open up the possibility of using such compounds for the efficient recognition of anions in pure water.

PROCESS OF PREPARING A FLUORIDE OF TETRAVLENT URANIUM

DOEpatents

Wheelwright, E.J.

1959-02-17

A method is described for producing a fluoride salt pf tetravalent uranium suitable for bomb reduction to metallic uranium. An aqueous solution of uranyl nitrate is treated with acetic acid and a nitrite-suppressor and then contacted with metallic lead whereby uranium is reduced from the hexavalent to the tetravalent state and soluble lead acetate is formed. Sulfate ions are then added to the solution to precipitate and remove the lead values. Hydrofluoric acid and alkali metal ions are then added causing the formation of an alkali metal uranium double-fluoride in which the uranium is in the tetravalent state. After recovery, this precipitate is suitable for using in the limited production of metallic uranium.

Structural Phase Transitions and Water Dynamics in Uranyl Fluoride Hydrates

DOE PAGES

Miskowiec, Andrew J.; Kirkegaard, Marie C.; Huq, Ashfia; ...

2015-11-17

We report a novel production method for uranium oxy uoride [(UO 2) 7F 14(H 2O) 7] 4H 2O, referred to as structure D. Structure D is produced as a product of hydrating anhydrous uranyl uoride, UO 2F 2, through the gas phase at ambient temperatures fol- lowed by desiccation by equilibration with a dry environment. We follow the structure of [(UO 2) 7F 14(H 2O) 7] 4H 2O through an intermediate, liquid-like phase, wherein the coordination number of the uranyl ion is reduced to 5 (from 6 in the anhydrous struc- ture), and a water molecule binds as an equatorialmore » ligand to the uranyl ion. Quasielas- tic neutron scattering results compare well with previous measurements of mineral hydrates. The two groups of structurally distinct water molecules in D perform re- stricted motion on a length scale commensurate with the O{H bond (r = 0.92 A). The more tightly bound equatorial ligand waters rotate slower (Dr = 2.2 ps -1) than their hydrogen-bonded partners (Dr = 28.7 ps -1).« less

METHOD FOR DISSOLVING ZIRCONIUM-URANIUM COMPOSITIONS

DOEpatents

Gens, T.A.

1961-07-18

A method is descrioed for treating a zirconium-- uranium composition to form a stable solution from which uranium and other values may be extracted by contacting the composition with at least a 4 molar aqueous solution of ammonium fluoride at a temperature of about 100 deg C, adding a peroxide, in incremental amounts, to the heated solution throughout the period of dissolution until all of the uranium is converted to soluble uranyl salt, adding nitric acid to the resultant solution to form a solvent extraction feed solution to convert the uranyl salt to a solvent extractable state, and thereafter recovering the uranium and other desired values from the feed solution by solvent extraction.

WET FLUORIDE SEPARATION METHOD

DOEpatents

Seaborg, G.T.; Gofman, J.W.; Stoughton, R.W.

1958-11-25

The separation of U/sup 233/ from thorium, protactinium, and fission products present in neutron-irradiated thorium is accomplished by dissolving the irradiated materials in aqueous nitric acid, adding either a soluble fluoride, iodate, phosphate, or oxalate to precipltate the thorium, separating the precipltate from the solution, and then precipitating uranlum and protactinium by alkalizing the solution. The uranium and protactinium precipitate is removcd from the solution and dissolved in nitric acid. The uranyl nitrate may then be extracted from the acid solution by means of ether, and the protactinium recovered from the aqueous phase.

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

PubMed

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.

76 FR 28336 - Domestic Licensing of Source Material-Amendments/Integrated Safety Analysis

Federal Register 2010, 2011, 2012, 2013, 2014

2011-05-17

... considered. The HF gas (and uranyl fluoride) is quickly produced from the chemical reaction that occurs when... worker's death was the inhalation of HF gas, which was produced from the chemical reaction of UF6 and..., would address both the radiological and chemical hazards from licensed material and hazardous chemicals...

PROCESS FOR SEPARATION OF HEAVY METALS

DOEpatents

Duffield, R.B.

1958-04-29

A method is described for separating plutonium from aqueous acidic solutions of neutron-irradiated uranium and the impurities associated therewith. The separation is effected by adding, to the solution containing hexavalent uranium and plutonium, acetate ions and the ions of an alkali metal and those of a divalent metal and thus forming a complex plutonium acetate salt which is carried by the corresponding complex of uranium, such as sodium magnesium uranyl acetate. The plutonium may be separated from the precipitated salt by taking the same back into solution, reducing the plutonium to a lower valent state on reprecipitating the sodium magnesium uranyl salt, removing the latter, and then carrying the plutonium from ihe solution by means of lanthanum fluoride.

Quasielastic neutron scattering with in situ humidity control: Water dynamics in uranyl fluoride

DOE PAGES

Miskowiec, A.; Kirkegaard, M. C.; Herwig, K. W.; ...

2016-03-04

The authors confirm that water vapor pressure is the driving thermodynamic force for the conversion of the anhydrous structure to [(UO 2F 2)(H 2O)] 7 ∙ (H 2O) 4, and they demonstrate the feasibility of extending this approach to aqueous forms of UO 2F 2+ xH 2O. This method has general applicability to systems in which water content itself is a driving variable for structural or dynamical phase transitions.

Movable-molybdenum-reflector reactivity experiments for control studies of compact space power reactor concepts

NASA Technical Reports Server (NTRS)

Fox, T. A.

1973-01-01

An experimental reflector reactivity study was made with a compact cylindrical reactor using a uranyl fluoride - water fuel solution. The reactor was axially unreflected and radially reflected with segments of molybdenum. The reflector segments were displaced incrementally in both the axial and radial dimensions, and the shutdown of each configuration was measured by using the pulsed-neutron source technique. The reactivity effects for axial and radial displacement of reflector segments are tabulated separately and compared. The experiments provide data for control-system studies of compact-space-power-reactor concepts.

PRODUCTION OF URANIUM

DOEpatents

Ruehle, A.E.; Stevenson, J.W.

1957-11-12

An improved process is described for the magnesium reduction of UF/sub 4/ to produce uranium metal. In the past, there have been undesirable premature reactions between the Mg and the bomb liner or the UF/sub 4/ before the actual ignition of the bomb reaction. Since these premature reactions impair the yield of uranium metal, they have been inhibited by forming a protective film upon the particles of Mg by reacting it with hydrated uranium tetrafluoride, sodium bifluoride, uranyl fluoride, or uranium trioxide. This may be accomplished by adding about 0.5 to 2% of the additive to the bomb charge.

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

Anderson, Brian B.; Kirkegaard, Marie C.; Miskowiec, Andrew J.

Uranyl fluoride (UO 2F 2) is a hygroscopic powder with two main structural phases: an anhydrous crystal and a partially hydrated crystal of the same R¯3m symmetry. The formally closed-shell electron structure of anhydrous UO 2F 2 is amenable to density functional theory calculations. We use density functional perturbation theory (DFPT) to calculate the vibrational frequencies of the anhydrous crystal structure and employ complementary inelastic neutron scattering and temperature-dependent Raman scattering to validate those frequencies. As a model closed-shell actinide, we investigated the effect of LDA, GGA, and non-local vdW functionals as well as the spherically-averaged Hubbard +U correction onmore » vibrational frequencies, electronic structure, and geometry of anhydrous UO 2F 2. A particular choice of U eff = 5.5 eV yields the correct U Oyl bond distance and vibrational frequencies for the characteristic Eg and A1g modes that are within the resolution of experiment. Inelastic neutron scattering and Raman scattering suggest a degree of water coupling to the lattice vibrations in the more experimentally accessible partially hydrated UO 2F 2 system, with the symmetric O-U-O stretching vibration shifted approximately 47 cm -1 lower in energy compared to the anhydrous structure. Evidence of water interaction with the uranyl ion is present from a two-peak decomposition of the uranyl stretching vibration in the Raman spectra and anion hydrogen stretching vibrations in the inelastic neutron scattering spectra. A first-order dehydration phase transition temperature is definitively identified to be 125 °C using temperature-dependent Raman scattering.« less

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

PubMed

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.

BASIC PEROXIDE PRECIPITATION METHOD OF SEPARATING PLUTONIUM FROM CONTAMINANTS

DOEpatents

Seaborg, G.T.; Perlman, I.

1959-02-10

A process is described for the separation from each other of uranyl values, tetravalent plutonium values and fission products contained in an aqueous acidic solution. First the pH of the solution is adjusted to between 2.5 and 8 and hydrogen peroxide is then added to the solution causing precipitation of uranium peroxide which carries any plutonium values present, while the fission products remain in solution. Separation of the uranium and plutonium values is then effected by dissolving the peroxide precipitate in an acidic solution and incorporating a second carrier precipitate, selective for plutonium. The plutonium values are thus carried from the solution while the uranium remains flissolved. The second carrier precipitate may be selected from among the group consisting of rare earth fluorides, and oxalates, zirconium phosphate, and bismuth lihosphate.

Investigation of the effects of radiolytic-gas bubbles on the long-term operation of solution reactors for medical-isotope production

NASA Astrophysics Data System (ADS)

Souto Mantecon, Francisco Javier

One of the most common and important medical radioisotopes is 99Mo, which is currently produced using the target irradiation technology in heterogeneous nuclear reactors. The medical isotope 99Mo can also be produced from uranium fission using aqueous homogeneous solution reactors. In solution reactors, 99Mo is generated directly in the fuel solution, resulting in potential advantages when compared with the target irradiation process in heterogeneous reactors, such as lower reactor power, less waste heat, and reduction by a factor of about 100 in the generation of spent fuel. The commercial production of medical isotopes in solution reactors requires steady-state operation at about 200 kW. At this power regime, the formation of radiolytic-gas bubbles creates a void volume in the fuel solution that introduces a negative coefficient of reactivity, resulting in power reduction and instabilities that may impede reactor operation for medical-isotope production. A model has been developed considering that reactivity effects are due to the increase in the fuel-solution temperature and the formation of radiolytic-gas bubbles. The model has been validated against experimental results from the Los Alamos National Laboratory uranyl fluoride Solution High-Energy Burst Assembly (SHEBA), and the SILENE uranyl nitrate solution reactor, commissioned at the Commissariat a l'Energie Atomique, in Valduc, France. The model shows the feasibility of solution reactors for the commercial production of medical isotopes and reveals some of the important parameters to consider in their design, including the fuel-solution type, 235U enrichment, uranium concentration, reactor vessel geometry, and neutron reflectors surrounding the reactor vessel. The work presented herein indicates that steady-state operation at 200 kW can be achieved with a solution reactor consisting of 120 L of uranyl nitrate solution enriched up to 20% with 235U and a uranium concentration of 145 kg/m3 in a graphite-reflected cylindrical geometry.

Quasielastic neutron scattering with in situ humidity control: Water dynamics in uranyl fluoride

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

Miskowiec, A., E-mail: miskowiecaj@ornl.gov; Trowbridge, L.; Anderson, B.

2016-03-07

The structural phase diagram of uranyl fluoride (UO{sub 2}F{sub 2}), while incomplete, contains at least one anhydrous crystal structure and a second, zeolite-like structure with the formula [(UO{sub 2}F{sub 2})(H{sub 2}O)]{sub 7} ⋅ (H{sub 2}O){sub 4} that can be produced by adding water to the anhydrous structure. While traditional diffraction measurements can easily differentiate these crystals, additional aqueous structures (in general of the form UO{sub 2}F{sub 2} + xH{sub 2}O) have been proposed as well. We present results using a novel sample environment setup to intercalate water during a quasielastic neutron scattering measurement over the course of 86 h. Our sample environment allows low-pressure (<2 atm)more » humid air flow across the sample coupled with a system to control the relative humidity of this air flow between 10% and 70%. The water dynamics in UO{sub 2}F{sub 2} and [(UO{sub 2}F{sub 2})(H{sub 2}O)]{sub 7} ⋅ (H{sub 2}O){sub 4} are sufficiently different to distinguish them, with water in the latter executing a restricted diffusion (D = 2.7 × 10{sup −6} cm{sup 2}/s) within the structure's accessible pores (r = 3.17 Å) such that the dynamics can be used as a fingerprinting tool. We confirm that water vapor pressure is the driving thermodynamic force for the conversion of the anhydrous structure to [(UO{sub 2}F{sub 2})(H{sub 2}O)]{sub 7} ⋅ (H{sub 2}O){sub 4}, and we demonstrate the feasibility of extending this approach to aqueous forms of UO{sub 2}F{sub 2} + xH{sub 2}O. This method has general applicability to systems in which water content itself is a driving variable for structural or dynamical phase transitions.« less

Formic acid interaction with the uranyl(VI) ion: structural and photochemical characterization.

PubMed

Lucks, Christian; Rossberg, André; Tsushima, Satoru; Foerstendorf, Harald; Fahmy, Karim; Bernhard, Gert

2013-10-07

Complex formation between the uranyl(VI) ion and formic acid was studied by infrared absorption (IR) and X-ray absorption (EXAFS) spectroscopy as well as density functional theory (DFT) calculations. In contrast to the acetate ion which forms exclusively a bidentate complex with uranyl(VI), the formate ion binds to uranyl(VI) in a unidentate fashion. The photochemistry of the uranyl(VI)-formic acid system was explored by DFT calculations and photoreduction of uranyl(VI) in the presence of formic acid was found to occur via an intermolecular process, that is, hydrogen abstraction from hydrogenformate by the photo-excited uranyl(VI). There is no photo-induced decarboxylation of uranyl(VI) formate via an intramolecular process, presumably due to lack of a C=C double bond.

PREPARATION OF UO$sub 2$ FOR NUCLEAR REACTOR FUEL PELLETS

DOEpatents

Googin, J.M.

1962-06-01

A method is given for preparing high-density UO/sub 2/ compacts. An aqueous uranyl fluoride solution is contacted with an aqueous ammonium hydroxide solution at an ammonium to-uranium ratio of 25: 1 to 30:1 to form a precipitate. The precipitate is separated from the- mother liquor, dried, and contacted with steam at a uniform temperature within the range of 400 to 650 deg C to produce U/ sub 3/O/sub 8/. The U/sub 3/O/sub 8/ is red uced to UO/sub 2/ with hydrogen at a uniform temperature within the range of 550 to 600 deg C. The UO/sub 2/ is then compressed into compacts and sintered. High-density compacts are fabricated to close tolerances without use of a binder and without machining or grinding. (AEC)

Photochemical water oxidation and origin of nonaqueous uranyl peroxide complexes.

PubMed

McGrail, Brendan T; Pianowski, Laura S; Burns, Peter C

2014-04-02

Sunlight photolysis of uranyl nitrate and uranyl acetate solutions in pyridine produces uranyl peroxide complexes. To answer longstanding questions about the origin of these complexes, we conducted a series of mechanistic studies and demonstrate that these complexes arise from photochemical oxidation of water. The peroxo ligands are easily removed by protonolysis, allowing regeneration of the initial uranyl complexes for potential use in catalysis.

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

NASA Astrophysics Data System (ADS)

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 proportion of uranyl-Fh inner-sphere sorption complexes decreased relative to uranyl-ESHA or uranyl-SRFA complexes, which comprised up to ∼60% of the total uranyl in the systems studied. At pH 7.0, uranyl-NOM complexes were also present in the Fh-NOM aggregates in the concentration ranges of ESHA or SRFA considered; however, the proportion of these complexes was smaller at pH 7.0 than at pH 4.6 and did not increase significantly with increasing NOM concentration.

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

PubMed

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 oxygen density near the pyrophyllite surface is similar to the other cases, but the hydrogen density profile indicates reduced hydrogen bonding between adsorbed water molecules and the surface.

Uranyl ion coordination

USGS Publications Warehouse

Evans, H.T.

1963-01-01

A review of the known crystal structures containing the uranyl ion shows that plane-pentagon coordination is equally as prevalent as plane-square or plane-hexagon. It is suggested that puckered-hexagon configurations of OH - or H2O about the uranyl group will tend to revert to plane-pentagon coordination. The concept of pentagonal coordination is invoked for possible explanations of the complex crystallography of the natural uranyl hydroxides and the unusual behavior of polynuclear ions in hydrolyzed uranyl solutions.

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

PubMed

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.

Micro-SHINE Uranyl Sulfate Irradiations at the Linac

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

Youker, Amanda J.; Kalensky, Michael; Chemerisov, Sergey

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.

Composition for detecting uranyl

DOEpatents

Baylor, Lewis C.; Stephens, Susan M.

1995-01-01

A composition for detecting the presence and concentration of a substance such as uranyl, comprising an organohalide covalently bonded to an indicator for said substance. The composition has at least one active OH site for forming a complex with the substance to be detected. The composition is made by reacting equimolar amounts of the indicator and the organohalide in a polar organic solvent. The absorbance spectrum of the composition-uranyl complex is shifted with respect to the absorbance spectrum of the indicator-uranyl complex, to provide better spectral resolution for detecting uranyl.

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

PubMed

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.

Effects of aqueous uranyl speciation on the kinetics of microbial uranium reduction

DOE PAGES

Belli, Keaton M.; DiChristina, Thomas J.; Van Cappellen, Philippe; ...

2015-02-16

The ability to predict the success of the microbial reduction of soluble U(VI) to highly insoluble U(IV) as an in situ bioremediation strategy is complicated by the wide range of geochemical conditions at contaminated sites and the strong influence of aqueous uranyl speciation on the bioavailability and toxicity of U(VI) to metal-reducing bacteria. In order to determine the effects of aqueous uranyl speciation on uranium bioreduction kinetics, incubations and viability assays with Shewanella putrefaciens strain 200 were conducted over a range of pH and dissolved inorganic carbon (DIC), Ca 2+, and Mg 2+ concentrations. A speciation-dependent kinetic model was developedmore » to reproduce the observed time series of total dissolved uranium concentration over the range of geochemical conditions tested. The kinetic model yielded the highest rate constant for the reduction of uranyl non-carbonate species (i.e., the ‘free’ hydrated uranyl ion, uranyl hydroxides, and other minor uranyl complexes), indicating that they represent the most readily reducible fraction of U(VI) despite being the least abundant uranyl species in solution. In the presence of DIC, Ca 2+, and Mg 2+ is suppressed during the formation of more bioavailable uranyl non-carbonate species and resulted in slower bioreduction rates. At high concentrations of bioavailable U(VI), however, uranium toxicity to S. putrefaciens inhibited bioreduction, and viability assays confirmed that the concentration of non-carbonate uranyl species best predicts the degree of toxicity. The effect of uranium toxicity was accounted for by incorporating the free ion activity model of metal toxicity into the bioreduction rate law. These results demonstrate that, in the absence of competing terminal electron acceptors, uranium bioreduction kinetics can be predicted over a wide range of geochemical conditions based on the bioavailability and toxicity imparted on U(VI) by solution composition. Finally, these findings also imply that the concentration of uranyl non-carbonate species, despite being extremely low, is a determining factor controlling uranium bioreduction at contaminated sites.« less

Density functional theory and molecular dynamics study of the uranyl ion (UO₂)²⁺.

PubMed

Rodríguez-Jeangros, Nicolás; Seminario, Jorge M

2014-03-01

The detection of uranium is very important, especially in water and, more importantly, in the form of uranyl ion (UO₂)²⁺, which is one of its most abundant moieties. Here, we report analyses and simulations of uranyl in water using ab initio modified force fields for water with improved parameters and charges of uranyl. We use a TIP4P model, which allows us to obtain accurate water properties such as the boiling point and the second and third shells of water molecules in the radial distribution function thanks to a fictitious charge that corrects the 3-point models by reproducing the exact dipole moment of the water molecule. We also introduced non-bonded interaction parameters for the water-uranyl intermolecular force field. Special care was taken in testing the effect of a range of uranyl charges on the structure of uranyl-water complexes. Atomic charges of the solvated ion in water were obtained using density functional theory (DFT) calculations taking into account the presence of nitrate ions in the solution, forming a neutral ensemble. DFT-based force fields were calculated in such a way that water properties, such as the boiling point or the pair distribution function stand. Finally, molecular dynamics simulations of a water box containing uranyl cations and nitrate anions are performed at room temperature. The three peaks in the oxygen-oxygen radial distribution function for water were found to be kept in the presence of uranyl thanks to the improvement of interaction parameters and charges. Also, we found three shells of water molecules surrounding the uranyl ion instead of two as was previously thought.

Cleaving Off Uranyl Oxygens through Chelation: A Mechanistic Study in the Gas Phase

DOE PAGES

Abergel, Rebecca J.; de Jong, Wibe A.; Deblonde, Gauthier J. -P.; ...

2017-10-11

Recent efforts to activate the strong uranium-oxygen bonds in the dioxo uranyl cation have been limited to single oxo-group activation through either uranyl reduction and functionalization in solution, or by collision induced dissociation (CID) in the gas-phase, using mass spectrometry (MS). Here, we report and investigate the surprising double activation of uranyl by an organic ligand, 3,4,3-LI(CAM), leading to the formation of a formal U 6+ chelate in the gas-phase. The cleavage of both uranyl oxo bonds was experimentally evidence d by CID, using deuterium and 18O isotopic substitutions, and by infrared multiple photon dissociation (IRMPD) spectroscopy. Density functional theorymore » (DFT) computations predict that the overall reaction requires only 132 kJ/mol, with the first oxygen activation entailing about 107 kJ/mol. Here, combined with analysis of similar, but unreactive ligands, these results shed light on the chelation-driven mechanism of uranyl oxo bond cleavage, demonstrating its dependence on the presence of ligand hydroxyl protons available for direct interactions with the uranyl oxygens.« less

EXTRACTION OF URANYL NITRATE FROM AQUEOUS SOLUTIONS

DOEpatents

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

1957-12-10

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

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

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

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 usingmore » 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.« less

A Uranyl Peroxide Dimer in the Gas Phase

DOE PAGES

Dau, Phuong D.; Dau, Phuong V.; Rao, Linfeng; ...

2017-03-14

For this study, the gas-phase uranyl peroxide dimer, [(UO 2) 2(O2)(L) 2] 2+ where L = 2,2'-trifluoroethylazanediyl)bis(N,N'-dimethylacetamide), was synthesized by electrospray ionization of a solution of UO 2 2+ and L. Collision-induced dissociation of this dimer resulted in endothermic O atom elimination to give [(UO 2) 2(O)(L) 2] 2+, which was found to spontaneously react with water via exothermic hydrolytic chemisorption to yield [(UO 2) 2(OH) 2(L) 2] 2+. Density functional theory computations of the energies for the gas-phase reactions are in accord with observations. The structures of the observed uranyl dimer were computed, with that of the peroxide ofmore » particular interest, as a basis to evaluate the formation of condensed phase uranyl peroxides with bent structures. The computed dihedral angle in [(UO 2) 2(O 2)(L) 2] 2+ is 145°, indicating a substantial deviation from the planar structure with a dihedral angle of 180°. Energies needed to induce bending in the most elementary gas-phase uranyl peroxide complex, [(UO 2) 2(O 2)] 2+, were computed. It was found that bending from the lowest-energy planar structure to dihedral angles up to 140° required energies of <10 kJ/mol. The gas-phase results demonstrate the inherent stability of the uranyl peroxide moiety and support the notion that the uranyl-peroxide-uranyl structural unit is intrinsically planar, with only minor energy perturbations needed to form the bent structures found in studtite and uranyl peroxide nanostructures.« less

URANIUM PURIFICATION PROCESS

DOEpatents

Ruhoff, J.R.; Winters, C.E.

1957-11-12

A process is described for the purification of uranyl nitrate by an extraction process. A solution is formed consisting of uranyl nitrate, together with the associated impurities arising from the HNO/sub 3/ leaching of the ore, in an organic solvent such as ether. If this were back extracted with water to remove the impurities, large quantities of uranyl nitrate will also be extracted and lost. To prevent this, the impure organic solution is extracted with small amounts of saturated aqueous solutions of uranyl nitrate thereby effectively accomplishing the removal of impurities while not allowing any further extraction of the uranyl nitrate from the organic solvent. After the impurities have been removed, the uranium values are extracted with large quantities of water.

A Solution-Based Approach for Mo-99 Production: Considerations for Nitrate versus Sulfate Media

DOE PAGES

Youker, Amanda J.; Chemerisov, Sergey D.; Kalensky, Michael; ...

2013-01-01

Molybdenum-99 is the parent of Technetium-99m, which is used in nearly 80% of all nuclear medicine procedures. The medical community has been plagued by Mo-99 shortages due to aging reactors, such as the NRU (National Research Universal) reactor in Canada. There are currently no US producers of Mo-99, and NRU is scheduled for shutdown in 2016, which means that another Mo-99 shortage is imminent unless a potential domestic Mo-99 producer fills the void. Argonne National Laboratory is assisting two potential domestic suppliers of Mo-99 by examining the effects of a uranyl nitrate versus a uranyl sulfate target solution configuration onmore » Mo-99 production. Uranyl nitrate solutions are easier to prepare and do not generate detectable amounts of peroxide upon irradiation, but a high radiation field can lead to a large increase in pH, which can lead to the precipitation of fission products and uranyl hydroxides. Uranyl sulfate solutions are more difficult to prepare, and enough peroxide is generated during irradiation to cause precipitation of uranyl peroxide, but this can be prevented by adding a catalyst to the solution. A titania sorbent can be used to recover Mo-99 from a highly concentrated uranyl nitrate or uranyl sulfate solution; however, different approaches must be taken to prevent precipitation during Mo-99 production.« less

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

DOE PAGES

Dublet, Gabrielle; Lezama Pacheco, Juan; Bargar, John R.; ...

2017-07-14

As part of a larger study of the reactivity and mobility of uranyl (U(VI)O 2 2+) 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). Here, no evidence was found for reduction of uranyl by either form of NOM aftermore » 24 h of exposure.« less

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

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

Dublet, Gabrielle; Lezama Pacheco, Juan; Bargar, John R.

As part of a larger study of the reactivity and mobility of uranyl (U(VI)O 2 2+) 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). Here, no evidence was found for reduction of uranyl by either form of NOM aftermore » 24 h of exposure.« less

Uranyl interaction with the hydrated (001) basal face of gibbsite: a combined theoretical and spectroscopic study.

PubMed

Veilly, Edouard; Roques, Jérôme; Jodin-Caumon, Marie-Camille; Humbert, Bernard; Drot, Romuald; Simoni, Eric

2008-12-28

The sorption of uranyl cations and water molecules on the basal (001) face of gibbsite was studied by combining vibrational and fluorescence spectroscopies together with density functional theory (DFT) computations. Both the calculated and experimental values of O-H bond lengths for the gibbsite bulk are in good agreement. In the second part, water sorption with this surface was studied to take into account the influence of hydration with respect to the uranyl adsorption. The computed water configurations agreed with previously published molecular dynamics studies. The uranyl adsorption in acidic media was followed by time-resolved laser-induced fluorescence spectroscopy and Raman spectrometry measurements. The existence of only one kind of adsorption site for the uranyl cation was then indicated in good agreement with the DFT calculations. The computation of the uranyl adsorption has been performed by means of a bidentate interaction with two surface oxygen atoms. The optimized structures displayed strong hydrogen bonds between the surface and the -yl oxygen of uranyl. The uranium-surface bond strength depends on the protonation state of the surface oxygen atoms. The calculated U-O(surface) bond lengths range between 2.1-2.2 and 2.6-2.7 A for the nonprotonated and protonated surface O atoms, respectively.

Preparation of U.sub.3 O.sub.8

DOEpatents

Johnson, David R.

1980-01-01

A method is described for the preparation of U.sub.3 O.sub.8 nuclear fuel material by direct precipitation of uranyl formate monohydrate from uranyl nitrate solution. The uranyl formate monohydrate precipitate is removed, dried and calcined to produce U.sub.3 O.sub.8 having a controlled particle size distribution.

Structure and Reactivity of X-ray Amorphous Uranyl Peroxide, U 2O 7

DOE PAGES

Odoh, Samuel O.; Shamblin, Jacob; Colla, Christopher A.; ...

2016-03-14

Recent accidents resulting in worker injury and radioactive contamination occurred due to pressurization of uranium yellowcake drums produced in the western USA. The drums contained an unexpected X-ray amorphous reactive form of uranium oxide, U 2O7. Heating hydrated uranyl peroxides produced during in situ mining unintentionally produced U 2O 7. It is a hygroscopic anhydrous uranyl peroxide that reacts rapidly with water to release O 2 gas and form metaschoepite, a uranyl-oxide hydrate. Quantum chemical calculations indicate that the most stable U 2O 7 conformer consists of two bent (UO 2) 2+ uranyl ions bridged by a peroxide group bidentatemore » and parallel to each uranyl ion, and a μ2-O atom, resulting in charge neutrality. A pair distribution function from neutron total scattering supports this structural model. The reactivity of U 2O 7 in water and with water in air is much higher than other uranium oxides, and this can be both hazardous and potentially advantageous in the nuclear fuel cycle.« less

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

WANG,YIFENG; XU,HUIFANG

Correctly identifying the possible alteration products and accurately predicting their occurrence in a repository-relevant environment are the key for the source-term calculation in a repository performance assessment. Uraninite in uranium deposits has long been used as a natural analog to spent fuel in a repository because of their chemical and structural similarity. In this paper, a SEM/AEM investigation has been conducted on a partially alternated uraninite sample from a uranium ore deposit of Shinkolobwe of Congo. The mineral formation sequences were identified: uraninite {yields} uranyl hydrates {yields} uranyl silicates {yields} Ca-uranyl silicates or uraninite {yields} uranyl silicates {yields} Ca-uranyl silicates.more » Reaction-path calculations were conducted for the oxidative dissolution of spent fuel in a representative Yucca Mountain groundwater. The predicted sequence is in general consistent with the SEM observations. The calculations also show that uranium carbonate minerals are unlikely to become major solubility-controlling mineral phases in a Yucca Mountain environment. Some discrepancies between model predictions and field observations are observed. Those discrepancies may result from poorly constrained thermodynamic data for uranyl silicate minerals.« less

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

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

Youker, Amanda J.; Kalensky, Michael; Quigley, Kevin J.

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.

Theoretical insights into the uranyl adsorption behavior on vanadium carbide MXene

NASA Astrophysics Data System (ADS)

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.

Self-assembly of silver nanoparticles as high active surface-enhanced Raman scattering substrate for rapid and trace analysis of uranyl(VI) ions

NASA Astrophysics Data System (ADS)

Wang, Shaofei; Jiang, Jiaolai; Wu, Haoxi; Jia, Jianping; Shao, Lang; Tang, Hao; Ren, Yiming; Chu, Mingfu; Wang, Xiaolin

2017-06-01

A facile surface-enhanced Raman scattering (SERS) substrate based on the self-assembly of silver nanoparticles on the modified silicon wafer was obtained, and for the first time, an advanced SERS analysis method basing on this as-prepared substrate was established for high sensitive and rapid detection of uranyl ions. Due to the weakened bond strength of Odbnd Udbnd O resulting from two kinds of adsorption of uranyl species (;strong; and ;weak; adsorption) on the substrate, the ν1 symmetric stretch vibration frequency of Odbnd Udbnd O shifted from 871 cm- 1 (normal Raman) to 720 cm- 1 and 826 cm- 1 (SERS) along with significant Raman enhancement. Effects of the hydrolysis of uranyl ions on SERS were also investigated, and the SERS band at 826 cm- 1 was first used to approximately define the constitution of uranyl species at trace quantity level. Besides, the SERS intensity was proportional to the variable concentrations of uranyl nitrate ranging from 10- 7 to 10- 3 mol L- 1 with an excellent linear relation (R2 = 0.998), and the detection limit was 10- 7 mol L- 1. Furthermore, the related SERS approach involves low-cost substrate fabrication, rapid and trace analysis simultaneously, and shows great potential applications for the field assays of uranyl ions in the nuclear fuel cycle and environmental monitoring.

Equatorial coordination of uranyl: Correlating ligand charge donation with the O yl-U-O yl asymmetric stretch frequency

DOE PAGES

Gibson, John K.; de Jong, Wibe A.; van Stipdonk, Michael J.; ...

2017-10-14

In uranyl coordination complexes, UO 2(L) n 2+, uranium in the formally dipositive [O=U=O] 2+ moiety is coordinated by n neutral organic electron donor ligands, L. The extent of ligand electron donation, which results in partial reduction of uranyl and weakening of the U=O bonds, is revealed by the magnitude of the red-shift of the uranyl asymmetric stretch frequency, ν 3 . This phenomenon appears in gas-phase complexes in which uranyl is coordinated by electron donor ligands: the ν 3 red-shift increases as the number of ligands and their proton affinity (PA) increases. Because PA is a measure of themore » enthalpy change associated with a proton-ligand interaction, which is much stronger and of a different nature than metal ion-ligand bonding, it is not necessarily expected that ligand PAs should reliably predict uranyl-ligand bonding and the resulting ν 3 red-shift. In this study, ν 3 was measured for uranyl coordinated by ligands with a relatively broad range of PAs, revealing a surprisingly good correlation between PA and ν 3 frequency. From computed ν 3 frequencies for bare UO 2 cations and neutrals, it is inferred that the effective charge of uranyl in UO 2(L) n 2+ complexes can be reduced to near zero upon ligation by sufficiently strong charge-donor ligands. The basis for the correlation between ν 3 and ligand PAs, as well as limitations and deviations from it, are considered. It is demonstrated that the correlation evidently extends to a ligand that exhibits polydentate metal ion coordination.« less

Surface complexation model of uranyl sorption on Georgia kaolinite

USGS Publications Warehouse

Payne, T.E.; Davis, J.A.; Lumpkin, G.R.; Chisari, R.; Waite, T.D.

2004-01-01

The adsorption of uranyl on standard Georgia kaolinites (KGa-1 and KGa-1B) was studied as a function of pH (3-10), total U (1 and 10 ??mol/l), and mass loading of clay (4 and 40 g/l). The uptake of uranyl in air-equilibrated systems increased with pH and reached a maximum in the near-neutral pH range. At higher pH values, the sorption decreased due to the presence of aqueous uranyl carbonate complexes. One kaolinite sample was examined after the uranyl uptake experiments by transmission electron microscopy (TEM), using energy dispersive X-ray spectroscopy (EDS) to determine the U content. It was found that uranium was preferentially adsorbed by Ti-rich impurity phases (predominantly anatase), which are present in the kaolinite samples. Uranyl sorption on the Georgia kaolinites was simulated with U sorption reactions on both titanol and aluminol sites, using a simple non-electrostatic surface complexation model (SCM). The relative amounts of U-binding >TiOH and >AlOH sites were estimated from the TEM/EDS results. A ternary uranyl carbonate complex on the titanol site improved the fit to the experimental data in the higher pH range. The final model contained only three optimised log K values, and was able to simulate adsorption data across a wide range of experimental conditions. The >TiOH (anatase) sites appear to play an important role in retaining U at low uranyl concentrations. As kaolinite often contains trace TiO2, its presence may need to be taken into account when modelling the results of sorption experiments with radionuclides or trace metals on kaolinite. ?? 2004 Elsevier B.V. All rights reserved.

Fiber optic detector and method for using same for detecting chemical species

DOEpatents

Baylor, Lewis C.; Buchanan, Bruce R.

1995-01-01

An optical sensing device for uranyl and other substances, a method for making an optical sensing device and a method for chemically binding uranyl and other indicators to glass, quartz, cellulose and similar substrates. The indicator, such as arsenazo III, is immobilized on the substrate using a chemical binding process. The immobilized arsenazo III causes uranyl from a fluid sample to bind irreversibly to the substrate at its active sites, thus causing absorption of a portion of light transmitted through the substrate. Determination of the amount of light absorbed, using conventional means, yields the concentration of uranyl present in the sample fluid. The binding of uranyl on the substrate can be reversed by subsequent exposure of the substrate to a solution of 2,6-pyridinedicarboxylic acid. The chemical binding process is suitable for similarly binding other indicators, such as bromocresol green.

Dynamic interplay between uranyl phosphate precipitation, sorption, and phase evolution

DOE PAGES

Munasinghe, P. Sumudu; Elwood Madden, Megan E.; Brooks, Scott C.; ...

2015-04-17

We report that natural examples demonstrate uranyl-phosphate minerals can maintain extremely low levels of aqueous uranium in groundwaters due to their low solubility. Thus, greater understanding of the geochemical factors leading to uranyl phosphate precipitation may lead to successful application of phosphate-based remediation methods. However, the solubility of uranyl phosphate phases varies over >3 orders of magnitude, with the most soluble phases typically observed in lab experiments. To understand the role of common soil/sediment mineral surfaces in the nucleation and transformation of uranyl phosphate minerals under environmentally relevant conditions, we carried out batch experiments with goethite and mica at pHmore » 6 in mixed electrolyte solutions ranging from 1–800 μM U and 1–800 μM P. All experiments ended with uranium concentrations below the USEPA MCL for U, but with 2–3 orders of magnitude difference in uranium concentrations.« less

METHOD OF INHIBITING CORROSION IN URANYL SULFATE SOLUTIONS

DOEpatents

Bohlmann, E.G.; Griess, J.C. Jr.

1960-08-23

A method is given for treating a uranyl sulfate solution to inhibit the corrosiveness of the solution and elevate the phase separation temperature of the solution. Lithium sulfate is added to the solution in an amount ranging from 0.25 to 1.3 times the uranyl sulfate concentration. The corrosiveness of the solution with respect to stainless steel is substantially decreased by this means. This treatment also serves to raise the phase separation temperature of the solution (above 250 deg C), at which time the uranyl sulfate solution separates into two liquid phases of unequal uranium concentration and thus becomes unsuitable as nuclear reactor fuel.

Evaluation of alternatives for best available technology treatment and retreatment of uranium-contaminated solutions at the Paducah Gaseous Diffusion Plant C-400 Facility

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

Del Cul, G.D.

1991-02-01

The Paducah Gaseous Diffusion Plant C-400 Decontamination Facility generators aqueous solutions that originate in drum washing, machine parts and equipment cleaning, and other decontamination processes. In general, the waste contains uranyl, fluoride, carbonate, and nitrate ions, in addition to soaps, detergents, secondary contaminants, and particulate matter. The main contaminants are fluoride, technetium, uranium, and other heavy metals. In accordance with Department of Energy (DOE) Order 5400.5, the releases of radioactive materials must be as low as reasonably achievable and be below the derived concentration guide limits. To comply with the DOE order, an action plan was formulated. The action planmore » included a literature search to support best available technology evaluation of treatment alternatives, a quality assurance/quality control plan, suggestion of alternative treatment options, bench-scale test studies of the proposed treatment alternatives, and establishment of the final recommendation. Five major technologies were considered: precipitation/coprecipitation, reverse osmosis, ultrafiltration, supported liquid membranes, and ion exchange. Biosorption was also briefly considered. Based on C-400's requirements and facilities, the precipitation/coprecipitation process appears to be the best suited for use at the plant. Four different treatment options using the precipitation/coprecipitation technology were proposed. Bench-scale studies of all four options were suggested. Options 1 and 2 represent a combination of lime-softening and iron coprecipitation. Laboratory test evaluations were initiated and the results involving Options 1 and 2 reported here. 29 refs., 1 fig., 2 tabs.« less

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

PubMed

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.

Iron (III) Matrix Effects on Mineralization and Immobilization of Actinides

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

Cynthia-May S. Gong; Tyler A. Sullens; Kenneth R. Czerwinski

2006-01-01

Abstract - A number of models for the Yucca Mountain Project nuclear waste repository use studies of actinide sorption onto well-defined iron hydroxide materials. In the case of a waste containment leak, however, a complex interaction between dissolved waste forms and failed containment vessel components can lead to immediate precipitation of migratory iron and uranyl in the silicate rich near-field environment. Use of the Fe(III) and UO22+ complexing agent acetohydroxamic acid (AHA) as a colorimetric agent for visible spectrophotometry is well-known. Using the second derivative of these spectra a distinct shift in iron complexation in the presence of silicate ismore » seen that is not seen with uranyl or alone. Silica also decreases the ability of uranyl and ferric solutions to absorb hydroxide, hastening precipitation. These ferric silicate precipitates are highly amorphous and soluble. Precipitates formed in the presence of uranyl below ~1 mol% exhibit lower solubility than precipitates from up to 50 mol % and of uranyl silicates alone.« less

Potential New Ligand Systems for Binding Uranyl Ions in Seawater Environments

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

Arnold, John

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. Ourmore » 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.« less

Synthesis and characterization of heterometallic uranyl pyridinedicarboxylate compounds

NASA Astrophysics Data System (ADS)

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.

First Cationic Uranyl-Organic Framework with Anion-Exchange Capabilities.

PubMed

Bai, Zhuanling; Wang, Yanlong; Li, Yuxiang; Liu, Wei; Chen, Lanhua; Sheng, Daopeng; Diwu, Juan; Chai, Zhifang; Albrecht-Schmitt, Thomas E; Wang, Shuao

2016-07-05

By controlling the extent of hydrolysis during the self-assembly process of a zwitterionic-based ligand with uranyl cations, we observed a structural evolution from the neutral uranyl-organic framework [(UO2)2(TTTPC)(OH)O(COOH)]·1.5DMF·7H2O (SCU-6) to the first cationic uranyl-organic framework with the formula of [(UO2)(HTTTPC)(OH)]Br·1.5DMF·4H2O (SCU-7). The crystal structures of SCU-6 and SCU-7 are layers built with tetranuclear and dinuclear uranyl clusters, respectively. Exchangeable halide anions are present in the interlaminar spaces balancing the positive charge of layers in SCU-7. Therefore, SCU-7 is able to effectively remove perrhenate anions from aqueous solution. Meanwhile, the H2PO4(-)-exchanged SCU-7 material exhibits a moderate proton conductivity of 8.70 × 10(-5) S cm(-1) at 50 °C and 90% relative humidity, representing nearly 80 times enhancement compared to the original material.

URANIUM EXTRACTION

DOEpatents

Harrington, C.D.; Opie, J.V.

1958-07-01

The recovery of uranium values from uranium ore such as pitchblende is described. The ore is first dissolved in nitric acid, and a water soluble nitrate is added as a salting out agent. The resulting feed solution is then contacted with diethyl ether, whereby the bulk of the uranyl nitrate and a portion of the impurities are taken up by the ether. This acid ether extract is then separated from the aqueous raffinate, and contacted with water causing back extractioa of the uranyl nitrate and impurities into the water to form a crude liquor. After separation from the ether extract, this crude liquor is heated to about 118 deg C to obtain molten uranyl nitrate hexahydratc. After being slightly cooled the uranyl nitrate hexahydrate is contacted with acid free diethyl ether whereby the bulk of the uranyl nitrate is dissolved into the ethcr to form a neutral ether solution while most of the impurities remain in the aqueous waste. After separation from the aqueous waste, the resultant ether solution is washed with about l0% of its volume of water to free it of any dissolved impurities and is then contacted with at least one half its volume of water whereby the uranyl nitrate is extracted into the water to form an aqueous product solution.

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

Gibson, John K.; de Jong, Wibe A.; van Stipdonk, Michael J.

In uranyl coordination complexes, UO 2(L) n 2+, uranium in the formally dipositive [O=U=O] 2+ moiety is coordinated by n neutral organic electron donor ligands, L. The extent of ligand electron donation, which results in partial reduction of uranyl and weakening of the U=O bonds, is revealed by the magnitude of the red-shift of the uranyl asymmetric stretch frequency, ν 3 . This phenomenon appears in gas-phase complexes in which uranyl is coordinated by electron donor ligands: the ν 3 red-shift increases as the number of ligands and their proton affinity (PA) increases. Because PA is a measure of themore » enthalpy change associated with a proton-ligand interaction, which is much stronger and of a different nature than metal ion-ligand bonding, it is not necessarily expected that ligand PAs should reliably predict uranyl-ligand bonding and the resulting ν 3 red-shift. In this study, ν 3 was measured for uranyl coordinated by ligands with a relatively broad range of PAs, revealing a surprisingly good correlation between PA and ν 3 frequency. From computed ν 3 frequencies for bare UO 2 cations and neutrals, it is inferred that the effective charge of uranyl in UO 2(L) n 2+ complexes can be reduced to near zero upon ligation by sufficiently strong charge-donor ligands. The basis for the correlation between ν 3 and ligand PAs, as well as limitations and deviations from it, are considered. It is demonstrated that the correlation evidently extends to a ligand that exhibits polydentate metal ion coordination.« less

Solid state and aqueous behavior of uranyl peroxide cage clusters

NASA Astrophysics Data System (ADS)

Pellegrini, Kristi Lynn

Uranyl peroxide cage clusters include a large family of more than 50 published clusters of a variety of sizes, which can incorporate various ligands including pyrophosphate and oxalate. Previous studies have reported that uranyl clusters can be used as a method to separate uranium from a solid matrix, with potential applications in reprocessing of irradiated nuclear fuel. Because of the potential applications of these novel structures in an advanced nuclear fuel cycle and their likely presence in areas of contamination, it is important to understand their behavior in both solid state and aqueous systems, including complex environments where other ions are present. In this thesis, I examine the aqueous behavior of U24Pp 12, as well as aqueous cluster systems with added mono-, di-, and trivalent cations. The resulting solutions were analyzed using dynamic light scattering and ultra-small angle X-ray scattering to evaluate the species in solution. Precipitates of these systems were analyzed using powder X-ray diffraction, X-ray fluorescence spectrometry, and Raman spectroscopy. The results of these analyses demonstrate the importance of cation size, charge, and concentration of added cations on the aqueous behavior of uranium macroions. Specifically, aggregates of various sizes and shapes form rapidly upon addition of cations, and in some cases these aggregates appear to precipitate into an X-ray amorphous material that still contains U24Pp12 clusters. In addition, I probe aggregation of U24Pp12 and U60, another uranyl peroxide cage cluster, in mixed solvent water-alcohol systems. The aggregation of uranyl clusters in water-alcohol systems is a result of hydrogen bonding with polar organic molecules and the reduction of the dielectric constant of the system. Studies of aggregation of uranyl clusters also allow for comparison between the newer uranyl polyoxometalate family and century-old transition metal polyoxometalates. To complement the solution studies of uranyl cage clusters, solid state analyses of U24Pp12 are presented, including single crystal X-ray diffraction and preliminary single crystal neutron diffraction. Solid state analyses are used to probe the complicated bonding environments between U24Pp12 and crystallized counterions, giving further insight into the importance of cluster protonation and counterions in uranyl cluster systems. The combination of solid state and solution techniques provides information about the complicated nature of uranyl peroxide nanoclusters, and insight towards future applications of clusters in the advanced nuclear fuel cycle and the environment.

URANIUM PURIFICATION PROCESS

DOEpatents

Winters, C.E.

1957-11-12

A method for the preparation of a diethyl ether solution of uranyl nitrate is described. Previously the preparation of such ether solutions has been difficult and expensive, since crystalline uranyl nitrate hexahydrate dissolves very slowly in ether. An improved method for effecting such dissolution has been found, and it comprises adding molten uranyl nitrate hexahydrate at a temperature of 65 to 105 deg C to the ether while maintaining the temperature of the ether solvent below its boiling point.

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

PubMed

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.

FY-15 Progress Report on Cleanup of irradiated SHINE Target Solutions Containing 140g-U/L Uranyl Sulfate

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

Bennett, Megan E.; Bowers, Delbert L.; Vandegrift, George F.

2015-09-01

During FY 2012 and 2013, a process was developed to convert the SHINE Target Solution (STS) of irradiated uranyl sulfate (140 g U/L) to uranyl nitrate. This process is necessary so that the uranium solution can be processed by the UREX (Uranium Extraction) separation process, which will remove impurities from the uranium so that it can be recycled. The uranyl sulfate solution must contain <0.02 M SO 4 2- so that the uranium will be extractable into the UREXsolvent. In addition, it is desired that the barium content be below 0.0007 M, as this is the limit in the Resourcemore » Conservation and Recovery Act (RCRA).« less

Behavior of Colorado Plateau uranium minerals during oxidation

USGS Publications Warehouse

Garrels, Robert Minard; Christ, C.L.

1956-01-01

Uranium occurs as U(VI) and U(IV) in minerals of the Colorado Plateau ores. The number of species containing U(VI) is large, but only two U(IV) minerals are known from the Plateau: uraninite, and oxide, and coffinite, a hydroxy-silicate. These oxidize to yield U(VI) before reacting significantly with other mineral constituents. Crystal-structure analysis has shown that U(VI) invariable occurs as uranyl ion, UO2+2. Uranyl ion may form complex carbonate or sulfate ions with resulting soluble compounds, but only in the absence of quinquevalent vanadium, arsenic, or phosphorous. In the presence of these elements in the +5 valence state, the uranyl ion is fixed in insoluble layer compounds formed by union of uranyl ion with orthovanadate, orthophosphate, or orthoarsenate. Under favorable conditions UO2+2 may react to form the relatively insoluble rutherfordine, UO2CO3, or hydrated uranyl hydroxides. These are rarely found on the Colorado Plateau as opposed to their excellent development in other uraniferous areas, a condition which is apparently related to the semiarid climate and low water table of the Plateau. Uranium may also be fixed as uranyl silicate, but little is known about minerals of this kind. In the present study emphasis has been placed on a detailing of the chemical and crystal structural changes which occur in the oxidation paragenetic sequence.

Identification of Uranyl Minerals Using Oxygen K-Edge X Ray Absorption Spectroscopy

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

Ward, Jesse D.; Bowden, Mark E.; Resch, Charles T.

2016-03-01

Uranium analysis is consistently needed throughout the fuel cycle, from mining to fuel fabrication to environmental monitoring. Although most of the world’s uranium is immobilized as pitchblende or uraninite, there exists a plethora of secondary uranium minerals, nearly all of which contain the uranyl cation. Analysis of uranyl compounds can provide clues as to a sample’s facility of origin and chemical history. X-ray absorption spectroscopy is one technique that could enhance our ability to identify uranium minerals. Although there is limited chemical information to be gained from the uranium X-ray absorption edges, recent studies have successfully used ligand NEXAFS tomore » study the physical chemistry of various uranium compounds. This study extends the use of ligand NEXAFS to analyze a suite of uranium minerals. We find that major classes of uranyl compounds (carbonate, oxyhydroxide, silicate, and phosphate) exhibit characteristic lineshapes in the oxygen K-edge absorption spectra. As a result, this work establishes a library of reference spectra that can be used to classify unknown uranyl minerals.« less

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

NASA Astrophysics Data System (ADS)

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.

Modulating Uranium Binding Affinity in Engineered Calmodulin EF-Hand Peptides: Effect of Phosphorylation

PubMed Central

Pardoux, Romain; Sauge-Merle, Sandrine; Lemaire, David; Delangle, Pascale; Guilloreau, Luc; Adriano, Jean-Marc; Berthomieu, Catherine

2012-01-01

To improve our understanding of uranium toxicity, the determinants of uranyl affinity in proteins must be better characterized. In this work, we analyzed the contribution of a phosphoryl group on uranium binding affinity in a protein binding site, using the site 1 EF-hand motif of calmodulin. The recombinant domain 1 of calmodulin from A. thaliana was engineered to impair metal binding at site 2 and was used as a structured template. Threonine at position 9 of the loop was phosphorylated in vitro, using the recombinant catalytic subunit of protein kinase CK2. Hence, the T9TKE12 sequence was substituted by the CK2 recognition sequence TAAE. A tyrosine was introduced at position 7, so that uranyl and calcium binding affinities could be determined by following tyrosine fluorescence. Phosphorylation was characterized by ESI-MS spectrometry, and the phosphorylated peptide was purified to homogeneity using ion-exchange chromatography. The binding constants for uranyl were determined by competition experiments with iminodiacetate. At pH 6, phosphorylation increased the affinity for uranyl by a factor of ∼5, from Kd = 25±6 nM to Kd = 5±1 nM. The phosphorylated peptide exhibited a much larger affinity at pH 7, with a dissociation constant in the subnanomolar range (Kd = 0.25±0.06 nM). FTIR analyses showed that the phosphothreonine side chain is partly protonated at pH 6, while it is fully deprotonated at pH 7. Moreover, formation of the uranyl-peptide complex at pH 7 resulted in significant frequency shifts of the νas(P-O) and νs(P-O) IR modes of phosphothreonine, supporting its direct interaction with uranyl. Accordingly, a bathochromic shift in νas(UO2)2+ vibration (from 923 cm−1 to 908 cm−1) was observed upon uranyl coordination to the phosphorylated peptide. Together, our data demonstrate that the phosphoryl group plays a determining role in uranyl binding affinity to proteins at physiological pH. PMID:22870263

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

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

Orona, N.S.; Tasat, D.R., E-mail: deborah.tasat@unsam.edu.ar; School of Dentistry, University of Buenos Aires, M. T. de Alvear 2142

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{submore » 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 all the range of doses tested.« less

Protein scaffolds for selective enrichment of metal ions

DOEpatents

He, Chuan; Zhou, Lu; Bosscher, Michael

2016-02-09

Polypeptides comprising high affinity for the uranyl ion are provided. Methods for binding uranyl using such proteins are likewise provided and can be used, for example, in methods for uranium purification or removal.

Uranyl(VI) nitrate salts: modeling thermodynamic properties using the binding mean spherical approximation theory and determination of "fictive" binary data.

PubMed

Ruas, Alexandre; Bernard, Olivier; Caniffi, Barbara; Simonin, Jean-Pierre; Turq, Pierre; Blum, Lesser; Moisy, Philippe

2006-02-23

This work is aimed at a description of the thermodynamic properties of highly concentrated aqueous solutions of uranyl nitrate at 25 degrees C. A new resolution of the binding mean spherical approximation (BIMSA) theory, taking into account 1-1 and also 1-2 complex formation, is developed and used to reproduce, from a simple procedure, experimental uranyl nitrate osmotic coefficient variation with concentration. For better consistency of the theory, binary uranyl perchlorate and chloride osmotic coefficients are also calculated. Comparison of calculated and experimental values is made. The possibility of regarding the ternary system UO(2)(NO(3))(2)/HNO(3)/H(2)O as a "simple" solution (in the sense of Zdanovskii, Stokes, and Robinson) is examined from water activity and density measurements. Also, an analysis of existing uranyl nitrate binary data is proposed and compared with our obtained data. On the basis of the concept of "simple" solution, values for density and water activity for the binary system UO(2)(NO(3))(2)/H(2)O are proposed in a concentration range on which uranyl nitrate precipitates from measurements on concentrated solutions of the ternary system UO(2)(NO(3))(2)/HNO(3)/H(2)O. This new set of binary data is "fictive" in the sense that the real binary system is not stable chemically. Finally, a new, interesting predictive capability of the BIMSA theory is shown.

A procedure for quantitation of total oxidized uranium for bioremediation studies

USGS Publications Warehouse

Elias, Dwayne A.; Senko, John M.; Krumholz, Lee R.

2003-01-01

A procedure was developed for the quantitation of complexed U(VI) during studies on U(VI) bioremediation. These studies typically involve conversion of soluble or complexed U(VI) (oxidized) to U(IV) (the reduced form which is much less soluble). Since U(VI) freely exchanges between material adsorbed to the solid phase and the dissolved phase, uranium bioremediation experiments require a mass balance of U in both its soluble and adsorbed forms as well as in the reduced sediment bound phase. We set out to optimize a procedure for extraction and quantitation of sediment bound U(VI). Various extractant volumes to sediment ratios were tested and it was found that between 1:1 to 8:1 ratios (v/w) there was a steady increase in U(VI) recovered, but no change with further increases in v/w ratio.Various strengths of NaHCO3, Na-EDTA, and Na-citrate were used to evaluate complexed U(VI) recovery, while the efficiency of a single versus repeated extraction steps was compared with synthesized uranyl-phosphate and uranyl-hydroxide. Total recovery with 1 M NaHCO3 was 95.7% and 97.9% from uranyl-phosphate and uranyl-hydroxide, respectively, compared to 80.7% and 89.9% using 450 mM NaHCO3. Performing the procedure once yielded an efficiency of 81.1% and 92.3% for uranyl-phosphate and uranyl-hydroxide, respectively, as compared to three times. All other extractants yielded 7.9–82.0% in both experiments.

Evaluation of alternatives for best available technology treatment and retreatment of uranium-contaminated wastewater at the Paducah Gaseous Diffusion Plant C-400 Facility

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

Del Cul, G.D.; Osborne, P.E.; Beck, D.E.

1991-01-01

The Paducah Gaseous Diffusion Plant (PGDP) C-400 Decontamination Facility generates aqueous solutions that originate in drum washing, machine parts and equipment cleaning, and other decontamination processes. The chemical composition of the waste depends on the particular operation involved. In general, the waste contains uranyl, fluoride, carbonate, and nitrate ions, plus soaps, detergents, secondary contaminants, and particulate matter. The uranium content is rather variable ranging between 0.5 and 30 g/l. The main contaminants are fluoride, technetium, uranium, and other heavy metals. The plan included (1) a literature search to support best available technology (BAT) evaluation of treatment alternatives, (2) a qualitymore » assurance/quality control plan, (3) suggestion of alternative treatment options, (4) bench-scale tests studies of the proposed treatment alternatives, and (5) establishment of the final recommendation. The following report records the evaluation of items (1) to (3) of the action plan for the BAT evaluation of alternatives for the treatment and retreatment of uranium-contaminated wastewater at the PGDP C-400 treatment facility. After a thorough literature search, five major technologies were considered: (1) precipitation/coprecipitation, (2) reverse osmosis, (3) ultrafiltration, (4) supported liquid membranes, and (5) ion exchange. Biosorption was also considered, but as it is a fairly new technology with few demonstrations of its capabilities, it is mentioned only briefly in the report. Based on C-400's requirements and facilities, the precipitation/coprecipitation process appears to be the best suited for use at the plant. Four different treatment options using the precipitation/coprecipitation technology are proposed. Bench-scale studies of the four options are suggested. 37 refs.« less

Engineered nano-magnetic iron oxide-urea-activated carbon nanolayer sorbent for potential removal of uranium (VI) from aqueous solution

NASA Astrophysics Data System (ADS)

Mahmoud, Mohamed E.; Khalifa, Mohamed A.; El Wakeel, Yasser M.; Header, Mennatllah S.; Abdel-Fattah, Tarek M.

2017-04-01

A novel magnetic nanosorbent was designed using chemical grafting of nano-magnetite (Nano-Fe3O4) with nanolayer of activated carbon (AC) via urea intermediate for the formation of Nano-Fe3O4-Urea-AC. Characterizing was carried out using FT-IR, SEM, HR-TEM, TGA, point of zero charge (Pzc) and surface area analysis. The designed sorbent maintained its magnetic properties and nanosized structure in the range of 8.7-14.1 nm. The surface area was identified as 389 m2/g based on the BET method. Sorption of uranyl ions from aqueous solutions was studied and evaluated in different experimental conditions. Removal of uranyl ions increased with increasing in pH value and the maximum percentage removal was established at pH 5.0. The removal and sorption processes of uranyl ions by Nano-Fe3O4-Urea-AC sorbent were studied and optimized using the batch technique. The key variables affecting removal of uranyl ions were studied including the effect of the contact time, dosage of Nano-Fe3O4-Urea-AC sorbent, reaction temperature, initial uranyl ions concentration and interfering anions and cations.

Immobilization of selenate by iron in aqueous solution under anoxic conditions and the influence of uranyl

NASA Astrophysics Data System (ADS)

Puranen, Anders; Jonsson, Mats; Dähn, Rainer; Cui, Daqing

2009-08-01

In proposed high level radioactive waste repositories a large part of the spent nuclear fuel (SNF) canisters are commonly composed of iron. Selenium is present in spent nuclear fuel as a long lived fission product. This study investigates the influence of iron on the uptake of dissolved selenium in the form of selenate and the effect of the presence of dissolved uranyl on the above interaction of selenate. The iron oxide, and selenium speciation on the surfaces was investigated by Raman spectroscopy. X-ray Absorption Spectroscopy was used to determine the oxidation state of the selenium and uranium on the surfaces. Under the simulated groundwater conditions (10 mM NaCl, 2 mM NaHCO 3, <0.1 ppm O 2) the immobilized selenate was found to be reduced to oxidation states close to zero or lower and uranyl was found to be largely reduced to U(IV). The near simultaneous reduction of uranyl was found to greatly enhance the rate of selenate reduction. These findings suggest that the presence of uranyl being reduced by an iron surface could substantially enhance the rate of reduction of selenate under anoxic conditions relevant for a repository.

Tris-amidoximate uranyl complexes via η2 binding mode coordinated in aqueous solution shown by X-ray absorption spectroscopy and density functional theory methods.

PubMed

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.

Coordination characteristics of uranyl BBP complexes: Insights from an electronic structure analysis

DOE PAGES

Pemmaraju, Chaitanya Das; Copping, Roy; Smiles, Danil E.; ...

2017-03-21

Here, organic ligand complexes of lanthanide/actinide ions have been studied extensively for applications in nuclear fuel storage and recycling. Several complexes of 2,6-bis(2-benzimidazyl)pyridine (H2BBP) featuring the uranyl moiety have been reported recently, and the present study investigates the coordination characteristics of these complexes using density functional theory-based electronic structure analysis. In particular, with the aid of several computational models, the nonplanar equatorial coordination about uranyl, observed in some of the compounds, is studied and its origin traced to steric effects.

Proteogenomic insights into uranium tolerance of a Chernobyl's Microbacterium bacterial isolate.

PubMed

Gallois, Nicolas; Alpha-Bazin, Béatrice; Ortet, Philippe; Barakat, Mohamed; Piette, Laurie; Long, Justine; Berthomieu, Catherine; Armengaud, Jean; Chapon, Virginie

2018-04-15

Microbacterium oleivorans A9 is a uranium-tolerant actinobacteria isolated from the trench T22 located near the Chernobyl nuclear power plant. This site is contaminated with different radionuclides including uranium. To observe the molecular changes at the proteome level occurring in this strain upon uranyl exposure and understand molecular mechanisms explaining its uranium tolerance, we established its draft genome and used this raw information to perform an in-depth proteogenomics study. High-throughput proteomics were performed on cells exposed or not to 10μM uranyl nitrate sampled at three previously identified phases of uranyl tolerance. We experimentally detected and annotated 1532 proteins and highlighted a total of 591 proteins for which abundances were significantly differing between conditions. Notably, proteins involved in phosphate and iron metabolisms show high dynamics. A large ratio of proteins more abundant upon uranyl stress, are distant from functionally-annotated known proteins, highlighting the lack of fundamental knowledge regarding numerous key molecular players from soil bacteria. Microbacterium oleivorans A9 is an interesting environmental model to understand biological processes engaged in tolerance to radionuclides. Using an innovative proteogenomics approach, we explored its molecular mechanisms involved in uranium tolerance. We sequenced its genome, interpreted high-throughput proteomic data against a six-reading frame ORF database deduced from the draft genome, annotated the identified proteins and compared protein abundances from cells exposed or not to uranyl stress after a cascade search. These data show that a complex cellular response to uranium occurs in Microbacterium oleivorans A9, where one third of the experimental proteome is modified. In particular, the uranyl stress perturbed the phosphate and iron metabolic pathways. Furthermore, several transporters have been identified to be specifically associated to uranyl stress, paving the way to the development of biotechnological tools for uranium decontamination. Copyright © 2017. Published by Elsevier B.V.

Exploring New Assembly Modes of Uranyl Terephthalate: Templated Syntheses and Structural Regulation of a Series of Rare 2D → 3D Polycatenated Frameworks

DOE PAGES

Mei, Lei; Wang, Cong-zhi; Zhu, Liu-zheng; ...

2017-06-23

In this paper, the reaction of uranyl nitrate with terephthalic acid (H 2TP) under hydrothermal conditions in the presence of an organic base, 1,3-(4,4'-bispyridyl)propane (BPP) or 4,4'-bipyridine (BPY), provided four uranyl terephthalate compounds with different entangled structures by a pH-tuning method. [UO 2(TP) 1.5](H 2BPP) 0.5·2H 2O (1) obtained in a relatively acidic solution (final aqueous pH, 4.28) crystallizes in the form of a noninterpenetrated honeycomb-like two-dimensional network structure. An elevation of the solution pH (final pH, 5.21) promotes the formation of a dimeric uranyl-mediated polycatenated framework, [(UO 2) 2(μ-OH) 2(TP) 2] 2(H 2BPP) 2·4.5H 2O (2). Another new polycatenatedmore » framework with a monomeric uranyl unit, [(UO 2) 2(TP) 3](H 2BPP) (3), begins to emerge as a minor accompanying product of 2 when the pH is increased up to 6.61, and turns out to be a significant product at pH 7.00. When more rigid but small-size BPY molecules replace BPP molecules, [UO 2(TP) 1.5](H 2BPP) 0.5 (4) with a polycatenated framework similar to 3 was obtained in a relatively acidic solution (final pH, 4.81). The successful preparation of 2–4 represents the first report of uranyl–organic polycatenated frameworks derived from a simple H 2TP linker. Finally, a direct comparison between these polycatenated frameworks and previously reported uranyl terephthalate compounds suggests that the template and cavity-filling effects of organic bases (such as BPP or BPY), in combination with specific hydrothermal conditions, promote the formation of uranyl terephthalate polycatenated frameworks.« less

Preliminary experiments on the reduction of the uranyl ion to uraninite by carbonaceous substances

USGS Publications Warehouse

Breger, Irving A.; Moore, Richard T.

1955-01-01

An aqueous solution of uranyl sulfate containing a suspension of subbituminous coal has been heated at 210 C for three days. Examination of the coal at the end of the experiment showed it to contain 31.8 percent uranium recognizable as uraninite by a sharp, strong X-ray diffraction pattern. A similar experiment with degraded spruce wood also led to the formation of uraninite but in lesser quantity and with broader lines in the X-ray diffraction pattern. The ability of coal or wood to reduce the uranyl ion is a critical factor in the correlation of studies of uraniferous coals containing the uranyl ion with studies of uraninite-bearing coalified wood from the Colorado Plateau. Although these results are based an preliminary experiments, they are extremely important geochemically and warrant the development of the series of controlled studies that are proposed.

Surface catalysis of uranium(VI) reduction by iron(II)

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

Liger, E.; Charlet, L.; Van Cappellen, P.

1999-10-01

Colloidal hematite ({alpha}-Fe{sub 2}O{sub 3}) is used as model solid to investigate the kinetic effect of specific adsorption interactions on the chemical reduction of uranyl (U{sup VI}O{sub 2}{sup 2+}) by ferrous iron. Acid-base titrations and Fe(II) and uranyl adsorption experiments are performed on hematite suspensions, under O{sub 2}- and CO{sub 2}-free conditions. The results are explained in terms of a constant capacitance surface complexation model of the hematite-aqueous solution interface. Two distinct Fe(II) surface complexes are required to reproduce the data: ({equivalent{underscore}to}Fe{sup III}OFe{sup II}){sup +} (or {equivalent{underscore}to}Fe{sup III}OFe{sup II}(OH{sub 2}){sub n}{sup +}) and {equivalent{underscore}to}Fe{sup III}OFe{sup II}OH{sup 0} (or {equivalent{underscore}to}Fe{sup III}OFe{supmore » II}(OH{sub 2}){sub n{minus}1}OH{sup 0}). The latter complex represents a significant fraction of total adsorbed Fe(II) at pH {gt} 6.5. Uranyl binding to the hematite particles is characterized by a sharp adsorption edge between pH 4 and pH 5.5. Because of the absence of competing aqueous carbonate complexes, uranyl remains completely adsorbed at pH {gt} 7. A single mononuclear surface complex accounts for the adsorption of uranyl over the entire range of experimental conditions. Although thermodynamically feasible, no reaction between uranyl and Fe(II) is observed in homogeneous solution at pH 7.5, for periods of up to three days. In hematite suspensions, however, surface-bound uranyl reacts on a time scale of hours. Based on Fourier Transformed Infrared spectra, chemical reduction of U(VI) is inferred to be the mechanism responsible for the disappearance of uranyl. The kinetics of uranyl reduction are quantified by measuring the decrease with time of the concentration of U(VI) extractable from the hematite particles by NaHCO{sub 3}. In the presence of excess Fe(II), the initial rate of U(VI) reduction exhibits a first-order dependence on the concentration of adsorbed uranyl. The pseudo-first-order rate constant varies with pH (range, 6--7.5) and the total (dissolved + adsorbed) concentration of Fe(II) (range, 2--160 {micro}M). When analyzing the rate data in terms of the calculated surface speciation, the variability of the rate constant can be accounted for entirely by changes in the concentration of the Fe(II) monohydroxo surface complex {equivalent{underscore}to}Fe{sup III}OFe{sup II}OH{sup 0}. Therefore, the rate law is derived for the hematite-catalyzed reduction of uranyl by Fe(II), where the bimolecular rate constant {kappa} has a value of 399 {+-} 25 M{sup {minus}1} min{sup {minus}1} at 25 C. The hydroxo surface complex is the rate-controlling reductant species, because it provides the most favorable coordination environment in which electrons are removed from Fe(II). Natural particulate matter collected in the hypolimnion of a seasonally stratified lake also causes the rapid reduction of uranyl by Fe(II), Ferrihydrite, identified in the particulate matter by X-ray diffraction, is one possible mineral phase accelerating the reaction between U(VI) and Fe(II). At near-neutral pH and total Fe(II) levels less than 1 mM, the pseudo-first-order rate constants of chemical U(VI) reduction, measured in the presence of the hematite and lake particles, are of the same order of magnitude as the highest corresponding rate coefficients for enzymatic U(VI) reduction in bacterial cultures. Hence, based on the results of this study, surface-catalyzed U(VI) reduction by Fe(II) is expected to be a major pathway of uranium immobilization in a wide range of redox-stratified environments.« less

Uranyl peroxide enhanced nuclear fuel corrosion in seawater.

PubMed

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.

M4FT-15OR03100415 - Update on COF-based Adsorbent Survey

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

Mayes, Richard T.; Dai, Sheng

2015-02-01

This letter report provides an update on activities focused on generating nanoporous adsorbents involving covalent organic frameworks (COF) and zeolitic imidazolium frameworks (ZIF). The adsorbents have been generated and screened in a uranyl-spiked brine (6 ppm U) to understand uranyl-binding behavior. Porous organic polymers (POP) also qualify under this title and are similar to the COF PPN-6 that is discussed herein. Seven COF/POP and one 1 ZIF were synthesized and screened for uranyl adsorption. Seawater screening is on-going via batch testing while flow screening systems are being developed at PNNL.

Method for loading resin beds

DOEpatents

Notz, Karl J.; Rainey, Robert H.; Greene, Charles W.; Shockley, William E.

1978-01-01

An improved method of preparing nuclear reactor fuel by carbonizing a uranium loaded cation exchange resin provided by contacting a H.sup.+ loaded resin with a uranyl nitrate solution deficient in nitrate, comprises providing the nitrate deficient solution by a method comprising the steps of reacting in a reaction zone maintained between about 145.degree.-200.degree. C, a first aqueous component comprising a uranyl nitrate solution having a boiling point of at least 145.degree. C with a second aqueous component to provide a gaseous phase containing HNO.sub.3 and a reaction product comprising an aqueous uranyl nitrate solution deficient in nitrate.

Uranyl peroxide enhanced nuclear fuel corrosion in seawater

PubMed Central

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

2012-01-01

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. PMID:22308442

Molecular dynamics simulations of uranyl adsorption and structure on the basal surface of muscovite

DOE PAGES

Teich-McGoldrick, Stephanie L.; Greathouse, Jeffery A.; Cygan, Randall T.

2014-02-05

Anthropogenic activities have led to an increased concentration of uranium on the Earth’s surface and potentially in the subsurface with the development of nuclear waste repositories. Uranium is soluble in groundwater, and its mobility is strongly affected by the presence of clay minerals in soils and in subsurface sediments. We use molecular dynamics simulations to probe the adsorption of aqueous uranyl (UO 2 2+) ions onto the basal surface of muscovite, a suitable proxy for typically ultrafine-grained clay phases. Model systems include the competitive adsorption between potassium counterions and aqueous ions (0.1 M and 1.0 M UO 2Cl 2 ,more » 0.1 M NaCl). We find that for systems with potassium and uranyl ions present, potassium ions dominate the adsorption phenomenon. Potassium ions adsorb entirely as inner-sphere complexes associated with the ditrigonal cavity of the basal surface. Uranyl ions adsorb in two configurations when it is the only ion species present, and in a single configuration in the presence of potassium. Finally, the majority of adsorbed uranyl ions are tilted less than 45° relative to the muscovite surface, and are associated with the Si 4Al 2 rings near aluminum substitution sites.« less

Highly Sensitive and Selective Uranium Detection in Natural Water Systems Using a Luminescent Mesoporous Metal-Organic Framework Equipped with Abundant Lewis Basic Sites: A Combined Batch, X-ray Absorption Spectroscopy, and First Principles Simulation Investigation.

PubMed

Liu, Wei; Dai, Xing; Bai, Zhuanling; Wang, Yanlong; Yang, Zaixing; Zhang, Linjuan; Xu, Lin; Chen, Lanhua; Li, Yuxiang; Gui, Daxiang; Diwu, Juan; Wang, Jianqiang; Zhou, Ruhong; Chai, Zhifang; Wang, Shuao

2017-04-04

Uranium is not only a strategic resource for the nuclear industry but also a global contaminant with high toxicity. Although several strategies have been established for detecting uranyl ions in water, searching for new uranium sensor material with great sensitivity, selectivity, and stability remains a challenge. We introduce here a hydrolytically stable mesoporous terbium(III)-based MOF material compound 1, whose channels are as large as 27 Å × 23 Å and are equipped with abundant exposed Lewis basic sites, the luminescence intensity of which can be efficiently and selectively quenched by uranyl ions. The detection limit in deionized water reaches 0.9 μg/L, far below the maximum contamination standard of 30 μg/L in drinking water defined by the United States Environmental Protection Agency, making compound 1 currently the only MOF material that can achieve this goal. More importantly, this material exhibits great capability in detecting uranyl ions in natural water systems such as lake water and seawater with pH being adjusted to 4, where huge excesses of competing ions are present. The uranyl detection limits in Dushu Lake water and in seawater were calculated to be 14.0 and 3.5 μg/L, respectively. This great detection capability originates from the selective binding of uranyl ions onto the Lewis basic sites of the MOF material, as demonstrated by synchrotron radiation extended X-ray adsorption fine structure, X-ray adsorption near edge structure, and first principles calculations, further leading to an effective energy transfer between the uranyl ions and the MOF skeleton.

Crystal Chemistry of the Potassium and Rubidium Uranyl Borate Families Derived from Boric Acid Fluxes

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

Wang, Shuao; Alekseev, Evgeny V.; Stritzinger, Jared T.

2010-07-19

The reaction of uranyl nitrate with a large excess of molten boric acid in the presence of potassium or rubidium nitrate results in the formation of three new potassium uranyl borates, K{sub 2}[(UO{sub 2}){sub 2}B{sub 12}O{sub 19}(OH){sub 4}]·0.3H{sub 2}O (KUBO-1), K[(UO{sub 2}){sub 2}B{sub 10}O{sub 15}(OH){sub 5}] (KUBO-2), and K[(UO{sub 2}){sub 2}B{sub 10}O{sub 16}(OH){sub 3}]·0.7H{sub 2}O (KUBO-3) and two new rubidium uranyl borates Rb{sub 2}[(UO{sub 2}){sub 2}B{sub 13}O{sub 20}(OH){sub 5}] (RbUBO-1) and Rb[(UO{sub 2}){sub 2}B{sub 10}O{sub 16}(OH){sub 3}]·0.7H{sub 2}O (RbUBO-2). The latter is isotypic with KUBO-3. These compounds share a common structural motif consisting of a linear uranyl, UO{sub 2}{sup 2+},more » cation surrounded by BO{sub 3} triangles and BO{sub 4} tetrahedra to create an UO{sub 8} hexagonal bipyramidal environment around uranium. The borate anions bridge between uranyl units to create sheets. Additional BO{sub 3} triangles extend from the polyborate layers and are directed approximately perpendicular to the sheets. All of these compounds adopt layered structures. With the exception of KUBO-1, the structures are all centrosymmetric. All of these compounds fluoresce when irradiated with long-wavelength UV light. The fluorescence spectrum yields well-defined vibronically coupled charge-transfer features.« less

The in-plant evaluation of a uranium NDA system

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

Sprinkle, J.K. Jr.; Baxman, H.R.; Langner, D.G.

1979-12-31

The Los Alamos Scientific Laboratory has an unirradiated enriched uranium reprocessing facility. Various types of solutions are generated in this facility, including distillates and raffinates containing ppm of uranium and concentrated solutions with up to 400 grams U/t. In addition to uranyl nitrate and HNO{sub 3}, the solutions may also contain zirconium, niobium, fluoride, and small amounts of many metals. A uranium solution assay system (USAS) has been installed to allow accurate and more timely process control, accountability, and criticality data to be obtained. The USAS assays are made by a variety of techniques that depend upon state-of-the-art high-resolution Ge(Li)more » gamma-ray spectroscopy integrated with an interactive, user-oriented computer software package. Tight control of the system`s performance is maintained by constantly monitoring the USAS status. Daily measurement control sequences are required, and the user is forced by the software to perform these sequences. Routine assays require 400 or 1000 seconds for a precision of 0.5% over the concentration range of 5--400 g/t. A comparison of the USAS precision and accuracy with that obtained by traditional destructive analytical chemistry techniques (colorimetric and volumetric) is presented.« less

The in-plant evaluation of a uranium NDA system

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

Sprinkle, J.K. Jr.; Baxman, H.R.; Langner, D.G.

1979-01-01

The Los Alamos Scientific Laboratory has an unirradiated enriched uranium reprocessing facility. Various types of solutions are generated in this facility, including distillates and raffinates containing ppm of uranium and concentrated solutions with up to 400 grams U/t. In addition to uranyl nitrate and HNO{sub 3}, the solutions may also contain zirconium, niobium, fluoride, and small amounts of many metals. A uranium solution assay system (USAS) has been installed to allow accurate and more timely process control, accountability, and criticality data to be obtained. The USAS assays are made by a variety of techniques that depend upon state-of-the-art high-resolution Ge(Li)more » gamma-ray spectroscopy integrated with an interactive, user-oriented computer software package. Tight control of the system's performance is maintained by constantly monitoring the USAS status. Daily measurement control sequences are required, and the user is forced by the software to perform these sequences. Routine assays require 400 or 1000 seconds for a precision of 0.5% over the concentration range of 5--400 g/t. A comparison of the USAS precision and accuracy with that obtained by traditional destructive analytical chemistry techniques (colorimetric and volumetric) is presented.« less

XAFS investigation of polyamidoxime-bound uranyl contests the paradigm from small molecule studies

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

Mayes, Richard T.; Piechowicz, Marek; Lin, Zekai

In this study, limited resource availability and population growth have motivated interest in harvesting valuable metals from unconventional reserves, but developing selective adsorbents for this task requires structural knowledge of metal binding environments. Amidoxime polymers have been identified as the most promising platform for large-scale extraction of uranium from seawater. However, despite more than 30 years of research, the uranyl coordination environment on these adsorbents has not been positively identified. We report the first XAFS investigation of polyamidoxime-bound uranyl, with EXAFS fits suggesting a cooperative chelating model, rather than the tridentate or η 2 motifs proposed by small molecule andmore » computational studies. Samples exposed to environmental seawater also display a feature consistent with a μ 2-oxo-bridged transition metal in the uranyl coordination sphere, suggesting in situ formation of a specific binding site or mineralization of uranium on the polymer surface. These unexpected findings challenge several long-held assumptions and have significant implications for development of polymer adsorbents with high selectivity.« less

Insight into hydrogen bonding of uranyl hydroxide layers and capsules by use of 1H magic-angle spinning NMR spectroscopy [Insight into the hydrogen bonding for uranyl hydroxides using 1H MAS NMR spectroscopy

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

Alam, Todd M.; Liao, Zuolei; Nyman, May

Solid-state 1H magic-angle spinning (MAS) NMR was used to investigate local proton environments in anhydrous [UO 2(OH) 2] (α-UOH) and hydrated uranyl hydroxide [(UO 2) 4O(OH) 6·5H 2O (metaschoepite). For the metaschoepite material, proton resonances of the μ 2-OH hydroxyl and interlayer waters were resolved, with two-dimensional (2D) double-quantum (DQ) 1H– 1H NMR correlation experiments revealing strong dipolar interactions between these different proton species. The experimental NMR results were combined with first-principles CASTEP GIPAW (gauge including projector-augmented wave) chemical shift calculations to develop correlations between hydrogen-bond strength and observed 1H NMR chemical shifts. Furthermore, these NMR correlations allowed characterization ofmore » local hydrogen-bond environments in uranyl U 24 capsules and of changes in hydrogen bonding that occurred during thermal dehydration of metaschoepite.« less

XAFS investigation of polyamidoxime-bound uranyl contests the paradigm from small molecule studies

DOE PAGES

Mayes, Richard T.; Piechowicz, Marek; Lin, Zekai; ...

2015-11-12

In this study, limited resource availability and population growth have motivated interest in harvesting valuable metals from unconventional reserves, but developing selective adsorbents for this task requires structural knowledge of metal binding environments. Amidoxime polymers have been identified as the most promising platform for large-scale extraction of uranium from seawater. However, despite more than 30 years of research, the uranyl coordination environment on these adsorbents has not been positively identified. We report the first XAFS investigation of polyamidoxime-bound uranyl, with EXAFS fits suggesting a cooperative chelating model, rather than the tridentate or η 2 motifs proposed by small molecule andmore » computational studies. Samples exposed to environmental seawater also display a feature consistent with a μ 2-oxo-bridged transition metal in the uranyl coordination sphere, suggesting in situ formation of a specific binding site or mineralization of uranium on the polymer surface. These unexpected findings challenge several long-held assumptions and have significant implications for development of polymer adsorbents with high selectivity.« less

Sorption of uranium in uranyl nitrate solutions on strong cationic resins and its elution with ammonium sulfate. II. Effects of EDTA on thorium decontamination; Estudos de sorpcao de uranio contido em solucoes de nitrato de uranilo por resina cationica forte e sua eluicao com sulfato de amonio. Parte II: efeito de EDTA na descontaminacao do torio (in Portuguese)

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

Ribas, Antonio G.S.; Abrao, Alcidio

1970-05-15

This paper describes the studies of decontamination of thorium present as impurity in uranyl nitrate solutions, which was carried out through strong cationic resin where the thorium was partially retained. Then, the final decontamination was performed percolating the uranyl solution on a second cationic resin, after complexation of thorium (and other impurities) with EDTA. The thorium decontamination and the uranium retention were studied as a function of EDTA/U ratio, uranium concentration and acidity of the influent uranyl nitrate. The elution conditions were also studied as a function of eluent flow rate, concentration and acidity. Several tables and graphs showing themore » final results are included. (tr-auth)« less

Synthesis and characterization of new ion-imprinted polymer for separation and preconcentration of uranyl (UO2(2+)) ions.

PubMed

Ahmadi, Seyed Javad; Noori-Kalkhoran, Omid; Shirvani-Arani, Simindokht

2010-03-15

UO(2)(2+) ion-imprinted polymer materials used for solid-phase extraction were prepared by copolymerization of a ternary complex of uranyl ions with styrene and divinyl benzene in the presence of 2,2'-azobisisobutyronitrile. The imprinted particles were leached by HCl 6M. Various parameters in polymerization steps such as DVB/STY ratio, time of polymerization and temperature of polymerization were varied to achieve the most efficient uranyl-imprinted polymer. X-ray diffraction (XRD), infra-red spectroscopy (IR), thermo gravimetric analysis (TGA), UV-vis and nitrogen sorption were used to characterize the polymer particles. The XRD results showed that uranyl ions were completely removed from the polymer after leaching process. IR Analysis indicated that the N,N'-ethylenebis(pyridoxylideneiminato) remained intact in the polymer even after leaching. Some parameters such as pH, weight of the polymer, elution time, eluent volume and aqueous phase volume which affects the efficiency of the polymer were studied. (c) 2009 Elsevier B.V. All rights reserved.

Predicting Stability Constants for Uranyl Complexes Using Density Functional Theory

DOE PAGES

Vukovic, Sinisa; Hay, Benjamin P.; Bryantsev, Vyacheslav S.

2015-04-02

The ability to predict the equilibrium constants for the formation of 1:1 uranyl:ligand complexes (log K 1 values) provides the essential foundation for the rational design of ligands with enhanced uranyl affinity and selectivity. We also use density functional theory (B3LYP) and the IEFPCM continuum solvation model to compute aqueous stability constants for UO 2 2+ complexes with 18 donor ligands. Theoretical calculations permit reasonably good estimates of relative binding strengths, while the absolute log K 1 values are significantly overestimated. Accurate predictions of the absolute log K 1 values (root mean square deviation from experiment < 1.0 for logmore » K 1 values ranging from 0 to 16.8) can be obtained by fitting the experimental data for two groups of mono and divalent negative oxygen donor ligands. The utility of correlations is demonstrated for amidoxime and imide dioxime ligands, providing a useful means of screening for new ligands with strong chelate capability to uranyl.« less

Insight into hydrogen bonding of uranyl hydroxide layers and capsules by use of 1H magic-angle spinning NMR spectroscopy [Insight into the hydrogen bonding for uranyl hydroxides using 1H MAS NMR spectroscopy

DOE PAGES

Alam, Todd M.; Liao, Zuolei; Nyman, May; ...

2016-04-27

Solid-state 1H magic-angle spinning (MAS) NMR was used to investigate local proton environments in anhydrous [UO 2(OH) 2] (α-UOH) and hydrated uranyl hydroxide [(UO 2) 4O(OH) 6·5H 2O (metaschoepite). For the metaschoepite material, proton resonances of the μ 2-OH hydroxyl and interlayer waters were resolved, with two-dimensional (2D) double-quantum (DQ) 1H– 1H NMR correlation experiments revealing strong dipolar interactions between these different proton species. The experimental NMR results were combined with first-principles CASTEP GIPAW (gauge including projector-augmented wave) chemical shift calculations to develop correlations between hydrogen-bond strength and observed 1H NMR chemical shifts. Furthermore, these NMR correlations allowed characterization ofmore » local hydrogen-bond environments in uranyl U 24 capsules and of changes in hydrogen bonding that occurred during thermal dehydration of metaschoepite.« less

Uranium XAFS analysis of kidney from rats exposed to uranium

PubMed Central

Kitahara, Keisuke; Numako, Chiya; Terada, Yasuko; Nitta, Kiyohumi; Homma-Takeda, Shino

2017-01-01

The kidney is the critical target of uranium exposure because uranium accumulates in the proximal tubules and causes tubular damage, but the chemical nature of uranium in kidney, such as its chemical status in the toxic target site, is poorly understood. Micro-X-ray absorption fine-structure (µXAFS) analysis was used to examine renal thin sections of rats exposed to uranyl acetate. The U L III-edge X-ray absorption near-edge structure spectra of bulk renal specimens obtained at various toxicological phases were similar to that of uranyl acetate: their edge position did not shift compared with that of uranyl acetate (17.175 keV) although the peak widths for some kidney specimens were slightly narrowed. µXAFS measurements of spots of concentrated uranium in the micro-regions of the proximal tubules showed that the edge jump slightly shifted to lower energy. The results suggest that most uranium accumulated in kidney was uranium (VI) but a portion might have been biotransformed in rats exposed to uranyl acetate. PMID:28244440

Uranium XAFS analysis of kidney from rats exposed to uranium.

PubMed

Kitahara, Keisuke; Numako, Chiya; Terada, Yasuko; Nitta, Kiyohumi; Shimada, Yoshiya; Homma-Takeda, Shino

2017-03-01

The kidney is the critical target of uranium exposure because uranium accumulates in the proximal tubules and causes tubular damage, but the chemical nature of uranium in kidney, such as its chemical status in the toxic target site, is poorly understood. Micro-X-ray absorption fine-structure (µXAFS) analysis was used to examine renal thin sections of rats exposed to uranyl acetate. The U L III -edge X-ray absorption near-edge structure spectra of bulk renal specimens obtained at various toxicological phases were similar to that of uranyl acetate: their edge position did not shift compared with that of uranyl acetate (17.175 keV) although the peak widths for some kidney specimens were slightly narrowed. µXAFS measurements of spots of concentrated uranium in the micro-regions of the proximal tubules showed that the edge jump slightly shifted to lower energy. The results suggest that most uranium accumulated in kidney was uranium (VI) but a portion might have been biotransformed in rats exposed to uranyl acetate.

Unusual Versatility of the Filamentous, Diazotrophic Cyanobacterium Anabaena torulosa Revealed for Its Survival during Prolonged Uranium Exposure

PubMed Central

Chandwadkar, Pallavi; Nayak, Chandrani

2017-01-01

ABSTRACT Reports on interactions between cyanobacteria and uranyl carbonate are rare. Here, we present an interesting succession of the metabolic responses employed by a marine, filamentous, diazotrophic cyanobacterium, Anabaena torulosa for its survival following prolonged exposure to uranyl carbonate extending up to 384 h at pH 7.8 under phosphate-limited conditions. The cells sequestered uranium (U) within polyphosphates on initial exposure to 100 μM uranyl carbonate for 24 to 28 h. Further incubation until 120 h resulted in (i) significant degradation of cellular polyphosphates causing extensive chlorosis and cell lysis, (ii) akinete differentiation followed by (iii) extracellular uranyl precipitation. X-ray diffraction (XRD) analysis, fluorescence spectroscopy, X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) spectroscopy established the identity of the bioprecipitated uranium as a U(VI) autunite-type mineral, which settled at the bottom of the vessel. Surprisingly, A. torulosa cells resurfaced as small green flakes typical of actively growing colonies on top of the test solutions within 192 to 240 h of U exposure. A consolidated investigation using kinetics, microscopy, and physiological and biochemical analyses suggested a role of inducible alkaline phosphatase activity of cell aggregates/akinetes in facilitating the germination of akinetes leading to substantial regeneration of A. torulosa by 384 h of uranyl incubation. The biomineralized uranium appeared to be stable following cell regeneration. Altogether, our results reveal novel insights into the survival mechanism adopted by A. torulosa to resist sustained uranium toxicity under phosphate-limited oxic conditions. IMPORTANCE Long-term effects of uranyl exposure in cyanobacteria under oxic phosphate-limited conditions have been inadequately explored. We conducted a comprehensive examination of the metabolic responses displayed by a marine cyanobacterium, Anabaena torulosa, to cope with prolonged exposure to uranyl carbonate at pH 7.8 under phosphate limitation. Our results highlight distinct adaptive mechanisms harbored by this cyanobacterium that enabled its natural regeneration following extensive cell lysis and uranium biomineralization under sustained uranium exposure. Such complex interactions between environmental microbes such as Anabaena torulosa and uranium over a broader time range advance our understanding on the impact of microbial processes on uranium biogeochemistry. PMID:28258135

Uranyl coordination in ionic liquids: the competition between ionic liquid anions, uranyl counterions, and Cl- anions investigated by extended X-ray absorption fine structure and UV-visible spectroscopies and molecular dynamics simulations.

PubMed

Gaillard, C; Chaumont, A; Billard, I; Hennig, C; Ouadi, A; Wipff, G

2007-06-11

The first coordination sphere of the uranyl cation in room-temperature ionic liquids (ILs) results from the competition between its initially bound counterions, the IL anions, and other anions (e.g., present as impurities or added to the solution). We present a joined spectroscopic (UV-visible and extended X-ray absorption fine structure)-simulation study of the coordination of uranyl initially introduced either as UO2X2 salts (X-=nitrate NO3-, triflate TfO-, perchlorate ClO4-) or as UO2(SO4) in a series of imidazolium-based ILs (C4mimA, A-=PF6-, Tf2N-, BF4- and C4mim=1-methyl-3-butyl-imidazolium) as well as in the Me3NBuTf2N IL. The solubility and dissociation of the uranyl salts are found to depend on the nature of X- and A-. The addition of Cl- anions promotes the solubilization of the nitrate and triflate salts in the C4mimPF6 and the C4mimBF4 ILs via the formation of chloro complexes, also formed with other salts. The first coordination sphere of uranyl is further investigated by molecular dynamics (MD) simulations on associated versus dissociated forms of UO2X2 salts in C4mimA ILs as a function of A- and X- anions. Furthermore, the comparison of UO2Cl(4)2-, 2 X- complexes with dissociated X- anions, to the UO2X2, 4 Cl- complexes with dissociated chlorides, shows that the former is more stable. The case of fluoro complexes is also considered, as a possible result of fluorinated IL anion's degradation, showing that UO2F42- should be most stable in solution. In all cases, uranyl is found to be solvated as formally anionic UO2XnAmClp2-n-m-p complexes, embedded in a cage of stabilizing IL imidazolium or ammonium cations.

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

NASA Astrophysics Data System (ADS)

Popescu (Hoştuc), Ioana-Carmen; Petru, Filip; Humelnicu, Ionel; Mateescu, Marina; Militaru, Ecaterina; Humelnicu, Doina

2014-10-01

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.

Process for the extraction of technetium from uranium

DOEpatents

Gong, Cynthia-May S.; Poineau, Frederic; Czerwinski, Kenneth R.

2010-12-21

A spent fuel reprocessing method contacts an aqueous solution containing Technetium(V) and uranyl with an acidic solution comprising hydroxylamine hydrochloride or acetohydroxamic acid to reduce Tc(V) to Tc(II, and then extracts the uranyl with an organic phase, leaving technetium(II) in aqueous solution.

Negative Stains Containing Trehalose: Application to Tubular and Filamentous Structures

NASA Astrophysics Data System (ADS)

Harris, J. Robin; Gerber, Max; Gebauer, Wolfgang; Wernicke, Wolfgang; Markl, Jürgen

1996-02-01

Several examples are presented that show the successful application of uranyl acetate and ammonium molybdate negative staining in the presence of trehalose for TEM studies of filamentous and tubular structures. The principal benefit to be gained from the inclusion of trehalose stems from the considerably reduced flattening of the large tubular structures and the greater orientational freedom of single molecules due to an increased depth of the negative stain in the presence of trehalose. Trehalose is likely to provide considerable protection to protein molecules and their assemblies during the drying of negatively stained specimens. Some reduction in the excessive density imparted by uranyl acetate around large assemblies is also achieved. Nevertheless, in the presence of 1% (w/v) trehalose, it is desirable to increase the concentration of negative stain to 5% (w/v) for ammonium molybdate and to 4% for uranyl acetate to produce satisfactory image contrast. In general, the ammonium molybdate-trehalose negative stain is more satisfactory than the uranyl acetate-trehalose combination, because of the greater electron beam sensitivity of the uranyl negative stain. Reassembled taxol-stabilized pig brain microtubules, together with collagen fibrils, sperm tails, helical filaments, and reassociated hemocyanin (KLH2), all from the giant keyhole limpet Megathura crenulata, have been studied by negative staining in the presence of trehalose. In all cases satisfactory TEM imaging conditions were readily obtained on the specimens, as long as regions of excessively deep stain were avoided.

Inhibition of poly(ADP-ribose)polymerase-1 and DNA repair by uranium

PubMed Central

Cooper, Karen L.; Dashner, Erica J.; Tsosie, Ranalda; Cho, Young Mi; Lewis, Johnnye

2015-01-01

Uranium has radiological and non-radiological effects within biological systems and there is increasing evidence for genotoxic and carcinogenic properties attributable to uranium through its heavy metal properties. In this study, we report that low concentrations of uranium (as uranyl acetate; <10 μM) is not cytotoxic to human embryonic kidney cells or normal human keratinocytes; however, uranium exacerbates DNA damage and cytotoxicity induced by hydrogen peroxide, suggesting that uranium may inhibit DNA repair processes. Concentrations of uranyl acetate in the low micromolar range inhibited the zinc finger DNA repair protein poly(ADP-ribose) polymerase (PARP)-1 and caused zinc loss from PARP-1 protein. Uranyl acetate exposure also led to zinc loss from the zinc finger DNA repair proteins Xeroderma Pigmentosum, Complementation Group A (XPA) and aprataxin (APTX). In keeping with the observed inhibition of zinc finger function of DNA repair proteins, exposure to uranyl acetate enhanced retention of induced DNA damage. Co-incubation of uranyl acetate with zinc largely overcame the impact of uranium on PARP-1 activity and DNA damage. These findings present evidence that low concentrations of uranium can inhibit DNA repair through disruption of zinc finger domains of specific target DNA repair proteins. This may provide a mechanistic basis to account for the published observations that uranium exposure is associated with DNA repair deficiency in exposed human populations. PMID:26627003

Inhibition of poly(ADP-ribose)polymerase-1 and DNA repair by uranium.

PubMed

Cooper, Karen L; Dashner, Erica J; Tsosie, Ranalda; Cho, Young Mi; Lewis, Johnnye; Hudson, Laurie G

2016-01-15

Uranium has radiological and non-radiological effects within biological systems and there is increasing evidence for genotoxic and carcinogenic properties attributable to uranium through its heavy metal properties. In this study, we report that low concentrations of uranium (as uranyl acetate; <10 μM) is not cytotoxic to human embryonic kidney cells or normal human keratinocytes; however, uranium exacerbates DNA damage and cytotoxicity induced by hydrogen peroxide, suggesting that uranium may inhibit DNA repair processes. Concentrations of uranyl acetate in the low micromolar range inhibited the zinc finger DNA repair protein poly(ADP-ribose) polymerase (PARP)-1 and caused zinc loss from PARP-1 protein. Uranyl acetate exposure also led to zinc loss from the zinc finger DNA repair proteins Xeroderma Pigmentosum, Complementation Group A (XPA) and aprataxin (APTX). In keeping with the observed inhibition of zinc finger function of DNA repair proteins, exposure to uranyl acetate enhanced retention of induced DNA damage. Co-incubation of uranyl acetate with zinc largely overcame the impact of uranium on PARP-1 activity and DNA damage. These findings present evidence that low concentrations of uranium can inhibit DNA repair through disruption of zinc finger domains of specific target DNA repair proteins. This may provide a mechanistic basis to account for the published observations that uranium exposure is associated with DNA repair deficiency in exposed human populations. Copyright © 2015 Elsevier Inc. All rights reserved.

SEPARATION OF URANYL AND RUTHENIUM VALUES BY THE TRIBUTYL PHOSPHATE EXTRACTION PROCESS

DOEpatents

Wilson, A.S.

1961-05-01

A process is given for separating uranyl values from ruthenium values contained in an aqueous 3 to 4 M nitric acid solution. After the addition of hydrogen peroxide to obtain a concentration of 0.3 M, the uranium is selectively extracted with kerosene-diluted tributyl phosphate.

Probing hydrogen and halogen-oxo interactions in uranyl coordination polymers: a combined crystallographic and computational study

DOE PAGES

Carter, Korey P.; Kalaj, Mark; Kerridge, Andrew; ...

2018-01-01

Four uranyl compounds containing either benzoic acid ( 1 ), m -chlorobenzoic acid ( 2 ), m -bromobenzoic acid ( 3 ), or m -iodobenzoic acid ( 4 ) are described, and the latter two compounds are used to probe non-covalent interaction strengths via structural, vibrational, and computational means.

On the origin of the cation templated self-assembly of uranyl-peroxide nanoclusters.

PubMed

Miró, Pere; Pierrefixe, Simon; Gicquel, Mickaël; Gil, Adrià; Bo, Carles

2010-12-22

Uranyl-peroxide nanoclusters display different topologies based on square, pentagonal and hexagonal building blocks. Computed complexation energies of different cations (Li(+), Na(+), K(+), Rb(+), and Cs(+)) with [UO(2)(O(2))(H(2)O)](n) (n = 4, 5, and 6) macrocycles suggest a strong cation templating effect. The inherent bent structure of a U-O(2)-U model dimer is demonstrated and justified through the analysis of its electronic structure, as well as of the inherent curvature of the four-, five-, and six-uranyl macrocyles. The curvature is enhaced by cation coordination, which is suggested to be the driving force for the self-assembly of the nanocapsules.

ANALYTICAL METHOD FOR THE DETERMINATION OF BORON IN URANYL NITRATE SOLUTIONS

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

None

1962-01-01

A method was developed for the determination of boron in uranyl nitrate solutions. The boron is separated from uranium and other impurities by distillation of methyl borate. It is determined absorptiometrically by means of curcumin in the presence of orthochlorophenol, perchloric acid, and acetic anhydride. The limit of detection is judged to be not greater than 0.05 mu g, but is dependent on the purity of the reagents used. The coefficient of variation on 210 results at the 0.2 mu g boron level was 26% with a bias of -25%. The method may be applied to depleted uranyl nitrate solutionsmore » and uranium slag recovery liquors. (auth)« less

Biosensing for the Environment and Defence: Aqueous Uranyl Detection Using Bacterial Surface Layer Proteins

PubMed Central

Conroy, David J.R.; Millner, Paul A.; Stewart, Douglas I.; Pollmann, Katrin

2010-01-01

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+. PMID:22399904

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

PubMed

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.

Kinetics of triscarbonato uranyl reduction by aqueous ferrous iron: a theoretical study.

PubMed

Wander, Matthew C F; Kerisit, Sebastien; Rosso, Kevin M; Schoonen, Martin A A

2006-08-10

Uranium is a pollutant whose mobility is strongly dependent on its oxidation state. While U(VI) in the form of the uranyl cation is readily reduced by a range of natural reductants, by contrast complexation of uranyl by carbonate greatly reduces its reduction potential and imposes increased electron transfer (ET) distances. Very little is known about the elementary processes involved in uranium reduction from U(VI) to U(V) to U(IV) in general. In this study, we examine the theoretical kinetics of ET from ferrous iron to triscarbonato uranyl in aqueous solution. A combination of molecular dynamics (MD) simulations and density functional theory (DFT) electronic structure calculations is employed to compute the parameters that enter into Marcus' ET model, including the thermodynamic driving forces, reorganization energies, and electronic coupling matrix elements. MD simulations predict that two ferrous iron atoms will bind in an inner-sphere fashion to the three-membered carbonate ring of triscarbonato uranyl, forming the charge-neutral ternary Fe(2)UO(2)(CO(3))(3)(H(2)O)(8) complex. Through a sequential proton-coupled electron-transfer mechanism (PCET), the first ET step converting U(VI) to U(V) is predicted by DFT to occur with an electronic barrier that corresponds to a rate on the order of approximately 1 s(-1). The second ET step converting U(V) to U(IV) is predicted to be significantly endergonic. Therefore, U(V) is a stabilized end product in this ET system, in agreement with experiment.

Ultrasensitive detection of uranyl by graphene oxide-based background reduction and RCDzyme-based enzyme strand recycling signal amplification.

PubMed

Li, Ming-Hui; Wang, Yong-Sheng; Cao, Jin-Xiu; Chen, Si-Han; Tang, Xian; Wang, Xiao-Feng; Zhu, Yu-Feng; Huang, Yan-Qin

2015-10-15

We proposed a novel strategy which combines graphene oxide-based background reduction with RCDzyme-based enzyme strand recycling amplification for ultrahigh sensitive detection of uranyl. The RCDzyme is designed to contain a guanine (G)-rich sequence that replaces the partial sequence in an uranyl-specific DNAzyme. This multifunctional probe can act as the target recognition element, DNAzyme and the primer of signal amplification. The presence of UO2(2+) can induce the cleavage of the substrate strands in RCDzyme. Then, each released enzyme strand can hybridize with another substrate strands to trigger many cycles of the cleavage by binding uranyl, leading to the formation of more G-quadruplexes by split guanine-rich oligonucleotide fragments. The resulting G-quadruplexes could bind to N-methyl-mesoporphyrin IX (NMM), causing an amplified detection signal for the target uranyl. Next, graphene oxide-based background reduction strategy was further employed for adsorbing free ssDNA and NMM, thereby providing a proximalis zero-background signal. The combination of RCDzyme signal amplification and proximalis zero-background signal remarkably improves the sensitivity of this method, achieving a dynamic range of two orders of magnitude and giving a detection limit down to 86 pM, which is much lower than those of related literature reports. These achievements might be helpful in the design of highly sensitive analytical platform for wide applications in environmental and biomedical fields. Copyright © 2015 Elsevier B.V. All rights reserved.

Effects of maleic acid and uranyl on mercurial diuresis in dogs

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

Nigrovic, V.; Koechel, D.A.; Cafruny, E.J.

1973-01-01

The effects of two nephrotoxic agents were studied in anesthetized dogs undergoing mercurial diuresis. One of the agents, uranyl, accumulates in the kidneys when administered as the acetate salt but does not readily react with sulfhydryl groups. In acute experiments uranyl acetate in doses up to 5 ..mu..mol/kg produced no change in the urinary excretion of sodium or chloride. Uranyl acetate given before the injection of mercury(II) did not reduce the diuretic response to inorganic mercury. The other compound, maleic acid, accumulates in the kidneys and also reacts readily with sulfhydryl groups. The administration of small doses of maleic acidmore » did not change the excretion of sodium but it decreased the excretion of chloride. The administration of maleic acid either before or after the administration of mercury completely abolished the diuretic response. The inhibition occurred without significant changes in urinary pH. Diuretic responses to ethacrynic acid, furosemide, hydrochlorothiazide or acetazolamide were preserved in maleate-treated dogs. Both the lack of any effect of uranyl on mercurial diuresis and the specific inhibition of mercurial diuresis by maleic acid support the presently accepted view that the renal diuretic receptor for mercury(II) has at least one sulfhydryl binding site. Although the inhibition is ascribed to competition between mercury(II) and maleate for binding on the receptor, it is conceivable that the reduction in urinary chloride excretion produced by maleate may be responsible, in part, for refractoriness to mercury(II).« less

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

PubMed

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.

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

PubMed

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.

Infrared Multiphoton Dissociation Spectroscopy of a Gas-Phase Complex of Uranyl and 3-Oxa-Glutaramide: An Extreme Red-Shift of the [O=U=O]²⁺ Asymmetric Stretch

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

Gibson, John K.; Hu, Hanshi; Van Stipdonk, Michael J.

2015-04-09

The gas-phase complex UO₂(TMOGA)₂²⁺ (TMOGA = tetramethyl-3-oxa-glutaramide) prepared by electrospray ionization was characterized by infrared multiphoton dissociation (IRMPD) spectroscopy. The IRMPD spectrum from 700–1800 cm⁻¹ was interpreted using a computational study based on density functional theory. The predicted vibrational frequencies are in good agreement with the measured values, with an average deviation of only 8 cm⁻¹ (<1%) and a maximum deviation of 21 cm⁻¹ (<2%). The only IR peak assigned to the linear uranyl moiety was the asymmetric ν₃ mode, which appeared at 965 cm⁻¹ and was predicted by DFT as 953 cm⁻¹. This ν₃ frequency is red-shifted relative tomore » bare uranyl, UO₂²⁺, by ca. 150 cm⁻¹ due to electron donation from the TMOGA ligands. Based on the degree of red-shifting, it is inferred that two TMOGA oxygen-donor ligands have a greater effective gas basicity than the four monodentate acetone ligands in UO₂(acetone)₄²⁺. The uranyl ν₃ frequency was also computed for uranyl coordinated by two TMGA ligands, in which the central Oether of TMOGA has been replaced by CH₂. The computed ν₃ for UO₂(TMGA)₂²⁺, 950 cm⁻¹, is essentially the same as that for UO₂(TMOGA)₂²⁺, suggesting that electron donation to uranyl from the Oether of TMOGA is minor. The computed ν₃ asymmetric stretching frequencies for the three actinyl complexes, UO₂(TMOGA)₂²⁺, NpO₂(TMOGA)₂²⁺ and PuO₂(TMOGA)₂²⁺, are comparable. This similarity is discussed in the context of the relationship between ν₃ and intrinsic actinide-oxygen bond energies in actinyl complexes.« less

Mixed-Ligand Uranyl Polyrotaxanes Incorporating a Sulfate/Oxalate Coligand: Achieving Structural Diversity via pH-Dependent Competitive Effect.

PubMed

Xie, Zhen-Ni; Mei, Lei; Hu, Kong-Qiu; Xia, Liang-Shu; Chai, Zhi-Fang; Shi, Wei-Qun

2017-03-20

A mixed-ligand system provides an alternative route to tune the structures and properties of metal-organic compounds by introducing functional organic or inorganic coligands. In this work, five new uranyl-based polyrotaxane compounds incorporating a sulfate or oxalate coligand have been hydrothermally synthesized via a mixed-ligand method. Based on C6BPCA@CB6 (C6BPCA = 1,1'-(hexane-1,6-diyl)bis(4-(carbonyl)pyridin-1-ium), CB6 = cucurbit[6]uril) ligand, UPS1 (UO 2 (L) 0.5 (SO 4 )(H 2 O)·2H 2 O, L = C6BPCA@CB6) is formed by the alteration of initial aqueous solution pH to a higher acidity. The resulting 2D uranyl polyrotaxane sheet structure of UPS1 is based on uranyl-sulfate ribbons connected by the C6BPCA@CB6 pseudorotaxane linkers. By using oxalate ligand instead of sulfate, four oxalate-containing uranyl polyrotaxane compounds, UPO1-UPO4, have been acquired by tuning reaction pH and ligand concentration: UPO1 (UO 2 (L) 0.5 (C 2 O 4 ) 0.5 (NO 3 )·3H 2 O) in one-dimensional chain was obtained at a low pH value range (1.47-1.89) and UPO2 (UO 2 (L)(C 2 O 4 )(H 2 O)·7H 2 O)obtained at a higher pH value range (4.31-7.21). By lowering the amount of oxalate, another two uranyl polyrotaxane network UPO3 ((UO 2 ) 2 (L) 0.5 (C 2 O 4 ) 2 (H 2 O)) and UPO4 ((UO 2 ) 2 O(OH)(L) 0.5 (C 2 O 4 ) 0.5 (H 2 O)) could be acquired at a low pH value of 1.98 and a higher pH value over 6, respectively. The UPO1-UPO4 compounds, which display structural diversity via pH-dependent competitive effect of oxalate, represent the first series of mixed-ligand uranyl polyrotaxanes with organic ligand as the coligand. Moreover, the self-assembly process and its internal mechanism concerning pH-dependent competitive effect and other related factors such as concentration of the reagents and coordination behaviors of the coligands were discussed in detail.

Unusual Versatility of the Filamentous, Diazotrophic Cyanobacterium Anabaena torulosa Revealed for Its Survival during Prolonged Uranium Exposure.

PubMed

Acharya, Celin; Chandwadkar, Pallavi; Nayak, Chandrani

2017-05-01

Reports on interactions between cyanobacteria and uranyl carbonate are rare. Here, we present an interesting succession of the metabolic responses employed by a marine, filamentous, diazotrophic cyanobacterium, Anabaena torulosa for its survival following prolonged exposure to uranyl carbonate extending up to 384 h at pH 7.8 under phosphate-limited conditions. The cells sequestered uranium (U) within polyphosphates on initial exposure to 100 μM uranyl carbonate for 24 to 28 h. Further incubation until 120 h resulted in (i) significant degradation of cellular polyphosphates causing extensive chlorosis and cell lysis, (ii) akinete differentiation followed by (iii) extracellular uranyl precipitation. X-ray diffraction (XRD) analysis, fluorescence spectroscopy, X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) spectroscopy established the identity of the bioprecipitated uranium as a U(VI) autunite-type mineral, which settled at the bottom of the vessel. Surprisingly, A. torulosa cells resurfaced as small green flakes typical of actively growing colonies on top of the test solutions within 192 to 240 h of U exposure. A consolidated investigation using kinetics, microscopy, and physiological and biochemical analyses suggested a role of inducible alkaline phosphatase activity of cell aggregates/akinetes in facilitating the germination of akinetes leading to substantial regeneration of A. torulosa by 384 h of uranyl incubation. The biomineralized uranium appeared to be stable following cell regeneration. Altogether, our results reveal novel insights into the survival mechanism adopted by A. torulosa to resist sustained uranium toxicity under phosphate-limited oxic conditions. IMPORTANCE Long-term effects of uranyl exposure in cyanobacteria under oxic phosphate-limited conditions have been inadequately explored. We conducted a comprehensive examination of the metabolic responses displayed by a marine cyanobacterium, Anabaena torulosa , to cope with prolonged exposure to uranyl carbonate at pH 7.8 under phosphate limitation. Our results highlight distinct adaptive mechanisms harbored by this cyanobacterium that enabled its natural regeneration following extensive cell lysis and uranium biomineralization under sustained uranium exposure. Such complex interactions between environmental microbes such as Anabaena torulosa and uranium over a broader time range advance our understanding on the impact of microbial processes on uranium biogeochemistry. Copyright © 2017 American Society for Microbiology.

Alteration, adsorption and nucleation processes on clay-water interfaces: Mechanisms for the retention of uranium by altered clay surfaces on the nanometer scale

NASA Astrophysics Data System (ADS)

Schindler, Michael; Legrand, Christine A.; Hochella, Michael F.

2015-03-01

Nano-scale processes on the solid-water interface of clay minerals control the mobility of metals in the environment. These processes can occur in confined pore spaces of clay buffers and barriers as well as in contaminated sediments and involve a combination of alteration, adsorption and nucleation processes of multiple species and phases. This study characterizes nano-scale processes on the interface between clay minerals and uranyl-bearing solution near neutral pH. Samples of clay minerals with a contact pH of ∼6.7 are collected from a U mill and mine tailings at Key Lake, Saskatchewan, Canada. The tailings material contains Cu-, As-, Co-, Mo-, Ni-, Se-bearing polymetallic phases and has been deposited with a surplus of Ca(OH)2 and Na2CO3 slaked lime. Small volumes of mill-process solutions containing sulfuric acid and U are occasionally discharged onto the surface of the tailings and are neutralized after discharge by reactions with the slaked lime. Transmission electron microscopy (TEM) in combination with the focused ion beam (FIB) technique and other analytical methods (SEM, XRD, XRF and ICP-OES) are used to characterize the chemical and mineralogical composition of phases within confined pore spaces of the clay minerals montmorillonite and kaolinite and in the surrounding tailings material. Alteration zones around the clay minerals are characterized by different generations of secondary silicates containing variable proportions of adsorbed uranyl- and arsenate-species and by the intergrowth of the silicates with the uranyl-minerals cuprosklodowskite, Cu[(UO2)2(SiO3OH)2](H2O)6 and metazeunerite, Cu[(UO2)(AsO4)2](H2O)8. The majority of alteration phases such as illite, illite-smectite, kaolinite and vermiculite have been most likely formed in the sedimentary basin of the U-ore deposit and contain low amounts of Fe (<5 at.%). Iron-enriched Al-silicates or illite-smectites (Fe >10 at.%) formed most likely in the limed tailings at high contact pH (∼10.5) and their structure is characterized by a low degree of long-range order. Adsorption of U and nucleation of metazeunerite and cuprosklodowskite are strongly controlled by the presence of the adsorbed oxy-anion species arsenate and silica on the Fe-enriched silicates. Heterogeneous nucleation of nano-crystals of the uranyl minerals occurs most likely on adsorption sites of binary uranyl-, arsenate- and silica-complexes as well as on ternary uranyl-arsenate or uranyl-silicate complexes. The uranyl minerals occur as aggregates of misoriented nano-size crystals and are the result of supersaturated solutions and a high number of nucleation sites that prevented the formation of larger crystals through Oswald ripening. The results of this study provide an understanding of interfacial nano-scale processes between uranyl species and altered clay buffers in a potential Nuclear Waste repository as similar alteration conditions of clays may occur in a multi-barrier system.

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

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

Arnold, John

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 tomore » 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.« less

Removal of toxic uranium from synthetic nuclear power reactor effluents using uranyl ion imprinted polymer particles.

PubMed

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.

Dehydration-driven evolution of topological complexity in ethylamonium uranyl selenates

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

Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru; Krivovichev, Sergey V.; Tananaev, Ivan G.

Single crystals of four novel uranyl selenate and selenite-selenate oxysalts with protonated ethylamine molecules, (C{sub 2}H{sub 8}N){sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)](H{sub 2}O) (I), (C{sub 2}H{sub 8}N){sub 3}[(UO{sub 2})(SeO{sub 4}){sub 2}(HSeO{sub 4})] (II), (C{sub 2}H{sub 8}N)[(UO{sub 2})(SeO{sub 4})(HSeO{sub 3})] (III), and (C{sub 2}H{sub 8}N)(H{sub 3}O)[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)] (IV) have been prepared by isothermal evaporation from aqueous solutions. Uranyl-containing 1D and 2D units have been investigated using topological approach and information-based complexity measurements that demonstrate the evolution of structural units and the increase of topological complexity with the decrease of H{sub 2}O content. - Graphical abstract: Single crystals ofmore » four novel uranyl selenate and selenite-selenate oxysalts with protonated ethylamine molecules have been prepared by isothermal evaporation from aqueous solutions. Structural analysis and information-based topological complexity calculations points to the possible sequence of crystalline phases formation, showing both topological and structural branches of evolution. - Highlights: • Single crystals of four novel uranyl oxysalts were prepared by evaporation method. • The graph theory was used for investigation of topologies of structural units. • Dehydration processes drives the evolution of topological complexity of 1D and 2D structural units.« less

SUMMARY TECHNICAL REPORT ON FEED MATERIALS FOR THE PERIOD APRIL 1, 1959 TO JUNE 30, 1959

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

Simmons, J.W. ed.

1959-07-20

Anaconda Acld, Kermac, Moab, Rifle, and Texas Zinc uranium concentrates were evaluated (the laboratory portlon of feed material evaluation). Laboratory equilibrium tests and Pilot Plant 2-inch-column extraction tests demonstrated effective distribution of uranium into a TBPkerosene solvent from aqueous phases containing as little as 0.5N HNO/sub 3/ and varying amounts of added metal nitrates (NaNO/sub 3/). The concentration of assoclated nitric acid in dilute aqueous nitric acld solutions was determined after values were obtained for the equillbrium constant for the reaction of tri-n-butyl phosphate with associated nitric acid and for the equilibrium distribution constant for the partition of associated nitricmore » acld into tri-n-butyl phosphate. Optimum partition of uranium into tri-n-butyl phosphate was realized in the laboratory by using an aqueous uranyl nitrate solution containing sufficient hydrogen ions to promote extraction and a low concentration of associated nitric acid. An Ohmart system for controlling the uranium profile in the A'' extractlon column was installed on Refinery pulse columns. Use of this system improved control but did not stop all column upsets. The effect of 13 to l89 ppm sodium contaminatlon upon hydrofluorination conversion of teraperature at the site of the reaction. Uranyl sulfate was shown to undergo an enantiotroplc transitlon at 755 deg C and to decompose to U/sub 3/O/sub 8/ in an atmosphere of oxygen sulfur dioxide, which gases are evolved during decoraposition. Decontamination of sodium, calcium, nickel, magnesium, gadolinium, and dysprosium was achieved in a laboratory investigatlon of the ADU process. UO/sub 2/ produced by reductions programmed from 700 to ll00 deg F was hydrofluorinated at programmed temperatures of 550 to 1100 deg F and isothermally at ll00 deg F. Good conversion was obtained for material whose source was ADU calcined at 1200 deg F. Uranium derbles were classified by the present method of derby grading and were then examined for slag coverage, slag volume, and slag weight. There was a high degree of overlap of these parameters for adjacent grades. A hydraulic separator for separatlng uranlum from magnesium and magnesium fluorlde was fabrlcated. Excellent separatlon was obtained for +l6 mesh material. A hydrochloric acid dissolution- UF/sub 4/ precipitation process for routing scrap materials to the reductlon-to- metal step was examined. The purification obtained was noted, and process conditions were varied to determine their effect upon UF/sub 4/ density, UF/sub 4/ purity and precipitation time. Three types of uranium scrap were subjected to the HCl dissolution-aqueous precipitation Winlo process to determine the purification achieved. Green salt made from dolomitlc bomb liner residues was found to be grossly contaminated. Acceptable green salt was raade from pickle liquor treated with formaldehyde and from pickle liquor plus black oxide. Nominal 80% yields were obtained in the recovery of magnesium metal by reaction of calcium carblde with magnesium fluoride slag and in the recovery of HF by the reactlon of sulfuric acid wlth magnesium fluoride slag. A sample holder for use in quantitative preferred orientation studies was fabricated. The holder, designed to fit a North American Philips Gonionweter, will accommodate specimens up to l 13/16 inches in diameter and incorporates a precision ball bearing. A satisfactory technique was developed for the analysis of uranium metal for traces of fluoride. A direct flame photometric method is glven for the determination of magnesium in uranium ore concentrates. No chemical separation step is required, except for high-iron-content ores. (auth)« less

FLAME DENITRATION AND REDUCTION OF URANIUM NITRATE TO URANIUM DIOXIDE

DOEpatents

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

1962-06-26

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

SHINE and Mini-SHINE Column Designs for Recovery of Mo from 140 g-U/L Uranyl Sulfate

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

Stepinski, Dominique C.; Vandegrift, George F.

Argonne is assisting SHINE Medical Technologies (SHINE) in their efforts to develop an accelerator-driven process that utilizes a uranyl-sulfate solution for the production of fission Mo-99. In an effort to design a Mo-recovery system for the SHINE project using low-enriched uranium (LEU), we conducted batch, breakthrough, and pulse tests to determine the Mo isotherm, mass-transfer zone (MTZ), and system parameters for a 130 g-U/L uranyl sulfate solution at pH 1 and 80°C, as described previously. The VERSE program was utilized to calculate the MTZ under various loading times and velocities. The results were then used to design Mo separation andmore » recovery columns employing a pure titania sorbent (110-μm particles, S110, and 60 Å pore size). The plant-scale column designs assume Mo will be separated from 271 L of a 141 g-U/L uranyl sulfate solution, pH 1, containing 0.0023 mM Mo. The VERSE-designed recovery systems have been tested and verified in laboratory-scale experiments, and this approach was found to be very successful.« less

Structure, Kinetics, and Thermodynamics of the Aqueous Uranyl(VI) Cation

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

Kerisit, Sebastien N.; Liu, Chongxuan

2013-08-20

Molecular simulation techniques are employed to gain insights into the structural, kinetic, and thermodynamic properties of the uranyl(VI) cation (UO22+) in aqueous solution. The simulations make use of an atomistic potential model (force field) derived in this work and based on the model of Guilbaud and Wipff (Guilbaud, P.; Wipff, G. J. Mol. Struct. (THEOCHEM) 1996, 366, 55-63). Reactive flux and thermodynamic integration calculations show that the derived potential model yields predictions for the water exchange rate and free energy of hydration, respectively, that are in agreement with experimental data. The water binding energies, hydration shell structure, and self-diffusion coefficientmore » are also calculated and discussed. Finally, a combination of metadynamics and transition path sampling simulations is employed to probe the mechanisms of water exchange reactions in the first hydration shell of the uranyl ion. These atomistic simulations indicate, based on two-dimensional free energy surfaces, that water exchanges follow an associative interchange mechanism. The nature and structure of the water exchange transition states are also determined. The improved potential model is expected to lead to more accurate predictions of uranyl adsorption energies at mineral surfaces using potential-based molecular dynamics simulations.« less

Selective colorimetric and fluorescent quenching determination of uranyl ion via its complexation with curcumin

NASA Astrophysics Data System (ADS)

Zhu, Jing-Hui; Zhao, Xin; Yang, Jidong; Tan, Yu-Ting; Zhang, Lei; Liu, Shao-Pu; Liu, Zhong-Fang; Hu, Xiao-Li

2016-04-01

Under pH 4.0 HAc-NaAc buffer medium, curcumin alone possesses extraordinary weak fluorescence emission. Nevertheless, the introduction of Triton X-100 micelles can largely enhance the fluorescence intensity of curcumin. Uranyl ions can complex with micelles-capped curcumin, along with the slight red shift of curcumin fluorescence (about 1-7 nm), a clear decrement of absorbance (424 nm) and fluorescence (507 nm) intensities, and a distinct color change from bright yellow to orange. The fluorescence decrements (ΔF, 507 nm) are positively correlated to the amount of uranyl ions in the concentration range of 3.7 × 10- 6-1.4 × 10- 5 mol L- 1. The detection limit of this fluorescence quenching methods is 3.7 × 10- 6 mol L- 1, which is nearly 9000 times lower than the maximum allowable level in drinking water proposed by World Health Organization. Good selectivity is achieved because of a majority of co-existing substances (such as Ce4 +, La3 +, and Th4 +) do not affect the detection. The content of uranyl ions in tap water samples was determined by the proposed method with satisfactory results.

Periodic density functional theory investigation of the uranyl ion sorption on three mineral surfaces: a comparative study.

PubMed

Roques, Jérôme; Veilly, Edouard; Simoni, Eric

2009-06-04

Canister integrity and radionuclides retention is of prime importance for assessing the long term safety of nuclear waste stored in engineered geologic depositories. A comparative investigation of the interaction of uranyl ion with three different mineral surfaces has thus been undertaken in order to point out the influence of surface composition on the adsorption mechanism(s). Periodic DFT calculations using plane waves basis sets with the GGA formalism were performed on the TiO(2)(110), Al(OH)(3)(001) and Ni(111) surfaces. This study has clearly shown that three parameters play an important role in the uranyl adsorption mechanism: the solvent (H(2)O) distribution at the interface, the nature of the adsorption site and finally, the surface atoms' protonation state.

Periodic Density Functional Theory Investigation of the Uranyl Ion Sorption on Three Mineral Surfaces: A Comparative Study

PubMed Central

Roques, Jérôme; Veilly, Edouard; Simoni, Eric

2009-01-01

Canister integrity and radionuclides retention is of prime importance for assessing the long term safety of nuclear waste stored in engineered geologic depositories. A comparative investigation of the interaction of uranyl ion with three different mineral surfaces has thus been undertaken in order to point out the influence of surface composition on the adsorption mechanism(s). Periodic DFT calculations using plane waves basis sets with the GGA formalism were performed on the TiO2(110), Al(OH)3(001) and Ni(111) surfaces. This study has clearly shown that three parameters play an important role in the uranyl adsorption mechanism: the solvent (H2O) distribution at the interface, the nature of the adsorption site and finally, the surface atoms’ protonation state. PMID:19582222

Sensitivity analysis of high resolution gamma-ray detection for safeguards monitoring at natural uranium conversion facilities

DOE PAGES

Dewji, Shaheen A.; Croft, Stephen; Hertel, Nolan E.

2016-12-16

Under the policies proposed by recent International Atomic Energy Agency (IAEA) circulars and policy papers, implementation of safeguards exists when any purified aqueous uranium solution or uranium oxides suitable for isotopic enrichment or fuel fabrication exists. Under IAEA Policy Paper 18, the starting point for nuclear material under safeguards was reinterpreted, suggesting that purified uranium compounds should be subject to safeguards procedures no later than the first point in the conversion process. In response to this technical need, a combination of simulation models and experimental measurements were employed in previous work to develop and validate gamma-ray nondestructive assay monitoring systemsmore » in a natural uranium conversion plant (NUCP). In particular, uranyl nitrate (UO 2(NO 3) 2) solution exiting solvent extraction was identified as a key measurement point (KMP). Passive nondestructive assay techniques using high resolution gamma-ray spectroscopy were evaluated to determine their viability as a technical means for drawing safeguards conclusions at NUCPs, and if the IAEA detection requirements of 1 significant quantity (SQ) can be met in a timely manner. Building upon the aforementioned previous validation work on detector sensitivity to varying concentrations of uranyl nitrate via a series of dilution measurements, this work investigates detector response parameter sensitivities to gamma-ray signatures of uranyl nitrate. The full energy peak efficiency of a detection system is dependent upon the sample, geometry, absorption, and intrinsic efficiency parameters. Perturbation of these parameters translates into corresponding variations of the 185.7 keV peak area of the 235U in uranyl nitrate. Such perturbations in the assayed signature impact the quality or versatility of the safeguards conclusions drawn. Given the potentially high throughput of uranyl nitrate in NUCPs, the ability to assay 1 SQ of material requires uncertainty «1%. Accounting for material self-shielding properties, pipe thickness, and source-detector orientation is instrumental in determining the robustness of gamma-ray detection in the process monitoring of uranyl nitrate in NUCPs. Monte Carlo models and ray-tracing models were employed to determine the sensitivity of the detected 185.7 keV photon to self-shielding properties, pipe thickness, and source-detector geometry. Considering the implementation of the detection of 1 SQ, diversion of 1 SQ becomes essentially undetectable given the systematic uncertainty, in addition to considerations such as propagating uncertainties due to pipe offset/position, as well as minor variations in pipe thickness. Consequently, pipe thickness was the most sensitive variable in affecting full energy efficiency of the 185.7 keV signature peak with up to 8% variation in efficiency for ±0.5 mm changes in Schedule 40 304L stainless steel piping. Furthermore, computation of the attenuation correction factor of the uranyl nitrate solution [CF(AT) (i.e. εsample)] using Parker's method using with the approximation for the geometrical factor κ≈π/4 was validated through experimental, Monte Carlo and ray-tracing calculations for a uranyl nitrate filled transfer pipe segment. Furthermore, quantifying sensitivity in detector position, as well as voiding effects due to bubbly flow or laminar flow with an air gap in the uranyl nitrate becomes increasingly important as considerations from (static) design-scale measurements translate into (dynamic) field operations tests.« less

Sensitivity analysis of high resolution gamma-ray detection for safeguards monitoring at natural uranium conversion facilities

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

Dewji, Shaheen A.; Croft, Stephen; Hertel, Nolan E.

Under the policies proposed by recent International Atomic Energy Agency (IAEA) circulars and policy papers, implementation of safeguards exists when any purified aqueous uranium solution or uranium oxides suitable for isotopic enrichment or fuel fabrication exists. Under IAEA Policy Paper 18, the starting point for nuclear material under safeguards was reinterpreted, suggesting that purified uranium compounds should be subject to safeguards procedures no later than the first point in the conversion process. In response to this technical need, a combination of simulation models and experimental measurements were employed in previous work to develop and validate gamma-ray nondestructive assay monitoring systemsmore » in a natural uranium conversion plant (NUCP). In particular, uranyl nitrate (UO 2(NO 3) 2) solution exiting solvent extraction was identified as a key measurement point (KMP). Passive nondestructive assay techniques using high resolution gamma-ray spectroscopy were evaluated to determine their viability as a technical means for drawing safeguards conclusions at NUCPs, and if the IAEA detection requirements of 1 significant quantity (SQ) can be met in a timely manner. Building upon the aforementioned previous validation work on detector sensitivity to varying concentrations of uranyl nitrate via a series of dilution measurements, this work investigates detector response parameter sensitivities to gamma-ray signatures of uranyl nitrate. The full energy peak efficiency of a detection system is dependent upon the sample, geometry, absorption, and intrinsic efficiency parameters. Perturbation of these parameters translates into corresponding variations of the 185.7 keV peak area of the 235U in uranyl nitrate. Such perturbations in the assayed signature impact the quality or versatility of the safeguards conclusions drawn. Given the potentially high throughput of uranyl nitrate in NUCPs, the ability to assay 1 SQ of material requires uncertainty «1%. Accounting for material self-shielding properties, pipe thickness, and source-detector orientation is instrumental in determining the robustness of gamma-ray detection in the process monitoring of uranyl nitrate in NUCPs. Monte Carlo models and ray-tracing models were employed to determine the sensitivity of the detected 185.7 keV photon to self-shielding properties, pipe thickness, and source-detector geometry. Considering the implementation of the detection of 1 SQ, diversion of 1 SQ becomes essentially undetectable given the systematic uncertainty, in addition to considerations such as propagating uncertainties due to pipe offset/position, as well as minor variations in pipe thickness. Consequently, pipe thickness was the most sensitive variable in affecting full energy efficiency of the 185.7 keV signature peak with up to 8% variation in efficiency for ±0.5 mm changes in Schedule 40 304L stainless steel piping. Furthermore, computation of the attenuation correction factor of the uranyl nitrate solution [CF(AT) (i.e. εsample)] using Parker's method using with the approximation for the geometrical factor κ≈π/4 was validated through experimental, Monte Carlo and ray-tracing calculations for a uranyl nitrate filled transfer pipe segment. Furthermore, quantifying sensitivity in detector position, as well as voiding effects due to bubbly flow or laminar flow with an air gap in the uranyl nitrate becomes increasingly important as considerations from (static) design-scale measurements translate into (dynamic) field operations tests.« less

Sensitivity analysis of high resolution gamma-ray detection for safeguards monitoring at natural uranium conversion facilities

NASA Astrophysics Data System (ADS)

Dewji, S. A.; Croft, S.; Hertel, N. E.

2017-03-01

Under the policies proposed by recent International Atomic Energy Agency (IAEA) circulars and policy papers, implementation of safeguards exists when any purified aqueous uranium solution or uranium oxides suitable for isotopic enrichment or fuel fabrication exists. Under IAEA Policy Paper 18, the starting point for nuclear material under safeguards was reinterpreted, suggesting that purified uranium compounds should be subject to safeguards procedures no later than the first point in the conversion process. In response to this technical need, a combination of simulation models and experimental measurements were employed in previous work to develop and validate gamma-ray nondestructive assay monitoring systems in a natural uranium conversion plant (NUCP). In particular, uranyl nitrate (UO2(NO3)2) solution exiting solvent extraction was identified as a key measurement point (KMP). Passive nondestructive assay techniques using high resolution gamma-ray spectroscopy were evaluated to determine their viability as a technical means for drawing safeguards conclusions at NUCPs, and if the IAEA detection requirements of 1 significant quantity (SQ) can be met in a timely manner. Building upon the aforementioned previous validation work on detector sensitivity to varying concentrations of uranyl nitrate via a series of dilution measurements, this work investigates detector response parameter sensitivities to gamma-ray signatures of uranyl nitrate. The full energy peak efficiency of a detection system is dependent upon the sample, geometry, absorption, and intrinsic efficiency parameters. Perturbation of these parameters translates into corresponding variations of the 185.7 keV peak area of the 235U in uranyl nitrate. Such perturbations in the assayed signature impact the quality or versatility of the safeguards conclusions drawn. Given the potentially high throughput of uranyl nitrate in NUCPs, the ability to assay 1 SQ of material requires uncertainty «1%. Accounting for material self-shielding properties, pipe thickness, and source-detector orientation is instrumental in determining the robustness of gamma-ray detection in the process monitoring of uranyl nitrate in NUCPs. Monte Carlo models and ray-tracing models were employed to determine the sensitivity of the detected 185.7 keV photon to self-shielding properties, pipe thickness, and source-detector geometry. Considering the implementation of the detection of 1 SQ, diversion of 1 SQ becomes essentially undetectable given the systematic uncertainty, in addition to considerations such as propagating uncertainties due to pipe offset/position, as well as minor variations in pipe thickness. Consequently, pipe thickness was the most sensitive variable in affecting full energy efficiency of the 185.7 keV signature peak with up to 8% variation in efficiency for ±0.5 mm changes in Schedule 40 304L stainless steel piping. Furthermore, computation of the attenuation correction factor of the uranyl nitrate solution [CF(AT) (i.e. εsample)] using Parker's method using with the approximation for the geometrical factor κ≈π/4 was validated through experimental, Monte Carlo and ray-tracing calculations for a uranyl nitrate filled transfer pipe segment. Quantifying sensitivity in detector position, as well as voiding effects due to bubbly flow or laminar flow with an air gap in the uranyl nitrate becomes increasingly important as considerations from (static) design-scale measurements translate into (dynamic) field operations tests.

Interaction of Uranium with Bacterial Cell Surfaces: Inferences from Phosphatase-Mediated Uranium Precipitation.

PubMed

Kulkarni, Sayali; Misra, Chitra Seetharam; Gupta, Alka; Ballal, Anand; Apte, Shree Kumar

2016-08-15

Deinococcus radiodurans and Escherichia coli expressing either PhoN, a periplasmic acid phosphatase, or PhoK, an extracellular alkaline phosphatase, were evaluated for uranium (U) bioprecipitation under two specific geochemical conditions (GCs): (i) a carbonate-deficient condition at near-neutral pH (GC1), and (ii) a carbonate-abundant condition at alkaline pH (GC2). Transmission electron microscopy revealed that recombinant cells expressing PhoN/PhoK formed cell-associated uranyl phosphate precipitate under GC1, whereas the same cells displayed extracellular precipitation under GC2. These results implied that the cell-bound or extracellular location of the precipitate was governed by the uranyl species prevalent at that particular GC, rather than the location of phosphatase. MINTEQ modeling predicted the formation of predominantly positively charged uranium hydroxide ions under GC1 and negatively charged uranyl carbonate-hydroxide complexes under GC2. Both microbes adsorbed 6- to 10-fold more U under GC1 than under GC2, suggesting that higher biosorption of U to the bacterial cell surface under GC1 may lead to cell-associated U precipitation. In contrast, at alkaline pH and in the presence of excess carbonate under GC2, poor biosorption of negatively charged uranyl carbonate complexes on the cell surface might have resulted in extracellular precipitation. The toxicity of U observed under GC1 being higher than that under GC2 could also be attributed to the preferential adsorption of U on cell surfaces under GC1. This work provides a vivid description of the interaction of U complexes with bacterial cells. The findings have implications for the toxicity of various U species and for developing biological aqueous effluent waste treatment strategies. The present study provides illustrative insights into the interaction of uranium (U) complexes with recombinant bacterial cells overexpressing phosphatases. This work demonstrates the effects of aqueous speciation of U on the biosorption of U and the localization pattern of uranyl phosphate precipitated as a result of phosphatase action. Transmission electron microscopy revealed that location of uranyl phosphate (cell associated or extracellular) was primarily influenced by aqueous uranyl species present under the given geochemical conditions. The data would be useful for understanding the toxicity of U under different geochemical conditions. Since cell-associated precipitation of metal facilitates easy downstream processing by simple gravity-based settling down of metal-loaded cells, compared to cumbersome separation techniques, the results from this study are of considerable relevance to effluent treatment using such cells. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Interaction of Uranium with Bacterial Cell Surfaces: Inferences from Phosphatase-Mediated Uranium Precipitation

PubMed Central

Kulkarni, Sayali; Misra, Chitra Seetharam; Gupta, Alka; Ballal, Anand

2016-01-01

ABSTRACT Deinococcus radiodurans and Escherichia coli expressing either PhoN, a periplasmic acid phosphatase, or PhoK, an extracellular alkaline phosphatase, were evaluated for uranium (U) bioprecipitation under two specific geochemical conditions (GCs): (i) a carbonate-deficient condition at near-neutral pH (GC1), and (ii) a carbonate-abundant condition at alkaline pH (GC2). Transmission electron microscopy revealed that recombinant cells expressing PhoN/PhoK formed cell-associated uranyl phosphate precipitate under GC1, whereas the same cells displayed extracellular precipitation under GC2. These results implied that the cell-bound or extracellular location of the precipitate was governed by the uranyl species prevalent at that particular GC, rather than the location of phosphatase. MINTEQ modeling predicted the formation of predominantly positively charged uranium hydroxide ions under GC1 and negatively charged uranyl carbonate-hydroxide complexes under GC2. Both microbes adsorbed 6- to 10-fold more U under GC1 than under GC2, suggesting that higher biosorption of U to the bacterial cell surface under GC1 may lead to cell-associated U precipitation. In contrast, at alkaline pH and in the presence of excess carbonate under GC2, poor biosorption of negatively charged uranyl carbonate complexes on the cell surface might have resulted in extracellular precipitation. The toxicity of U observed under GC1 being higher than that under GC2 could also be attributed to the preferential adsorption of U on cell surfaces under GC1. This work provides a vivid description of the interaction of U complexes with bacterial cells. The findings have implications for the toxicity of various U species and for developing biological aqueous effluent waste treatment strategies. IMPORTANCE The present study provides illustrative insights into the interaction of uranium (U) complexes with recombinant bacterial cells overexpressing phosphatases. This work demonstrates the effects of aqueous speciation of U on the biosorption of U and the localization pattern of uranyl phosphate precipitated as a result of phosphatase action. Transmission electron microscopy revealed that location of uranyl phosphate (cell associated or extracellular) was primarily influenced by aqueous uranyl species present under the given geochemical conditions. The data would be useful for understanding the toxicity of U under different geochemical conditions. Since cell-associated precipitation of metal facilitates easy downstream processing by simple gravity-based settling down of metal-loaded cells, compared to cumbersome separation techniques, the results from this study are of considerable relevance to effluent treatment using such cells. PMID:27287317

PROCESS OF SEPARATING URANIUM FROM AQUEOUS SOLUTION BY SOLVENT EXTRACTION

DOEpatents

Warf, J.C.

1958-08-19

A process is described for separating uranium values from aqueous uranyl nitrate solutions. The process consists in contacting the uramium bearing solution with an organic solvent, tributyl phosphate, preferably diluted with a less viscous organic liquida whereby the uranyl nitrate is extracted into the organic solvent phase. The uranvl nitrate may be recovered from the solvent phase bv back extracting with an aqueous mediuin.

PROCESS FOR EXTRACTING NEPTUNIUM AND PLUTONIUM FROM NITRIC ACID SOLUTIONS OF SAME CONTAINING URANYL NITRATE WITH A TERTIARY AMINE

DOEpatents

Sheppard, J.C.

1962-07-31

A process of selectively extracting plutonium nitrate and neptunium nitrate with an organic solution of a tertiary amine, away from uranyl nitrate present in an aqueous solution in a maximum concentration of 1M is described. The nitric acid concentration is adjusted to about 4M and nitrous acid is added prior to extraction. (AEC)

[La(UO{sub 2})V{sub 2}O{sub 7}][(UO{sub 2})(VO{sub 4})] the first lanthanum uranyl-vanadate with structure built from two types of sheets based upon the uranophane anion-topology

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

Mer, A.; Obbade, S.; Rivenet, M.

2012-01-15

The new lanthanum uranyl vanadate divanadate, [La(UO{sub 2})V{sub 2}O{sub 7}][(UO{sub 2})(VO{sub 4})] was obtained by reaction at 800 Degree-Sign C between lanthanum chloride, uranium oxide (U{sub 3}O{sub 8}) and vanadium oxide (V{sub 2}O{sub 5}) and the structure was determined from single-crystal X-ray diffraction data. This compound crystallizes in the orthorhombic system with space group P2{sub 1}2{sub 1}2{sub 1} and unit-cell parameters a=6.9470(2) A, b=7.0934(2) A, c=25.7464(6) A, V=1268.73(5) A{sup 3}, Z=4. A full matrix least-squares refinement yielded R{sub 1}=0.0219 for 5493 independent reflections. The crystal structure is characterized by the stacking of uranophane-type sheets {sup 2}{sub {infinity}}[(UO{sub 2})(VO{sub 4})]{sup -}more » and double layers {sup 2}{sub {infinity}}[La(UO{sub 2})(V{sub 2}O{sub 7})]{sup +} connected through La-O bonds involving the uranyl oxygen of the uranyl-vanadate sheets. The double layers result from the connection of two {sup 2}{sub {infinity}}[La(UO{sub 2})(VO{sub 4}){sub 2}]{sup -} sheets derived from the uranophane anion-topology by replacing half of the uranyl ions by lanthanum atoms and connected through the formation of divanadate entities. - Graphical abstract: A view of the three-dimensional structure of [La(UO{sub 2})V{sub 2}O{sub 7}][(UO{sub 2})(VO{sub 4})]. Highlights: Black-Right-Pointing-Pointer New lanthanum uranyl vanadate divanadate has been synthesized. Black-Right-Pointing-Pointer Structure was determined from single-crystal X-ray diffraction data. Black-Right-Pointing-Pointer Structure is characterized by uranophane-type sheets and double layers {sup 2}{sub {infinity}}[La(UO{sub 2})(V{sub 2}O{sub 7})]{sup +}.« less

Inhibition of poly(ADP-ribose)polymerase-1 and DNA repair by uranium

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

Cooper, Karen L.; Dashner, Erica J.; Tsosie, Ranalda

Uranium has radiological and non-radiological effects within biological systems and there is increasing evidence for genotoxic and carcinogenic properties attributable to uranium through its heavy metal properties. In this study, we report that low concentrations of uranium (as uranyl acetate; < 10 μM) is not cytotoxic to human embryonic kidney cells or normal human keratinocytes; however, uranium exacerbates DNA damage and cytotoxicity induced by hydrogen peroxide, suggesting that uranium may inhibit DNA repair processes. Concentrations of uranyl acetate in the low micromolar range inhibited the zinc finger DNA repair protein poly(ADP-ribose) polymerase (PARP)-1 and caused zinc loss from PARP-1 protein.more » Uranyl acetate exposure also led to zinc loss from the zinc finger DNA repair proteins Xeroderma Pigmentosum, Complementation Group A (XPA) and aprataxin (APTX). In keeping with the observed inhibition of zinc finger function of DNA repair proteins, exposure to uranyl acetate enhanced retention of induced DNA damage. Co-incubation of uranyl acetate with zinc largely overcame the impact of uranium on PARP-1 activity and DNA damage. These findings present evidence that low concentrations of uranium can inhibit DNA repair through disruption of zinc finger domains of specific target DNA repair proteins. This may provide a mechanistic basis to account for the published observations that uranium exposure is associated with DNA repair deficiency in exposed human populations. - Highlights: • Low micromolar concentration of uranium inhibits polymerase-1 (PARP-1) activity. • Uranium causes zinc loss from multiple DNA repair proteins. • Uranium enhances retention of DNA damage caused by ultraviolet radiation. • Zinc reverses the effects of uranium on PARP activity and DNA damage repair.« less

Cyanex based uranyl sensitive polymeric membrane electrodes.

PubMed

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.

Construction of Uranyl Selective Electrode Based on Complex of Uranyl Ion with New Ligand Carboxybenzotriazole in PVC Matrix Membrane

NASA Astrophysics Data System (ADS)

Abu-Dalo, M. A.; Al-Rawashdeh, N. A. F.; Al-Mheidat, I. R.; Nassory, N. S.

2015-10-01

In the present study uranyl selective electrodes in polyvinyl chloride (PVC) matrix membrane were prepared based on a complex of uranyl ion (UO2) with carboxybenzotriazole (CBT) as ligand. The effect of the nature of plasticizer in PVC matrix were evaluated using three different plasticizers, these are dibutyl phthalate (DBP), dioctyl phthalate (DOP) and bis(2-ethylhexyl) sebacate (BHS). The results of this study indicated that the best plasticizer could be used is the DBP, which may be attributed to its lowest viscosity value compared to DOP and BHS. The electrodes with DBP as plasticizer exhibits a Nernstian response with a slope of 28.0 mV/ decade, over a wide range of concentration from 3.0×10-5-6.0×10-2 M and a detection limit of 4.0×10-6 M. It can be used in the pH range of 4.0-10.0 with a response time of less than 10 s for DBP and 25 s for both DOP and BHS. The effects of ions interferences on the electrode response were evaluated. The di- and tri-valent cations were found to interfere less than univalent cations, which was attributed to the high diffusion and the exchange rate between the univalent ions and the uranyl ion solution. The electrodes were characterized by Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron microscopy (SEM). The results of the standard addition method were satisfactory with errors less than 7%. The developed electrode was found to be fast, sensitive and reliable indicated its potential use in measuring the uranly ion concentration in the field.

Incorporation of Np(V) and U(VI) in Carbonate and Sulfate Minerals Crystallized from Aqueous Solution

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

Balboni, Enrica; Morrison, Jessica M.; Wang, Zheming

2015-02-15

The neptunyl Np(V)O2 + and uranyl U(VI)O2 2+ ions are soluble in groundwater, although their interaction with minerals in the subsurface may impact their mobility. One mechanism for the immobilization of actinyl ions in the subsurface is coprecipitation in low-temperature minerals that form naturally, or that are induced to form as part of a remediation strategy. Important differences in the crystal-chemical behavior of the Np(V) neptunyl and U(VI) uranyl ions suggest their behavior towards incorporation into growing crystals may differ significantly. Using a selection of low temperature minerals synthesized in aqueous systems under ambient conditions, this study examines the factorsmore » that impact the structural incorporation of the Np(V) neptunyl and U(VI) uranyl ions in carbonate and sulfate minerals.« less

PROCESSES OF RECOVERING URANIUM FROM A CALUTRON

DOEpatents

Baird, D.O.; Zumwalt, L.R.

1958-07-15

An improved process is described for recovering the residue of a uranium compound which has been subjected to treatment in a calutron, from the parts of the calutron disposed in the source region upon which the residue is deposited. The process may be utilized when the uranium compound adheres to a surface containing metals of the group consisting of copper, iron, chromium, and nickel. The steps comprise washing the surface with an aqueous acidic oxidizing solvent for the uranium whereby there is obtained an acidic aqueous Solution containing uranium as uranyl ions and metals of said group as impurities, treating the acidic solution with sodium acetate in the presenee of added sodium nitrate to precipitate the uranium as sodium uranyl acetate away from the impurities in the solution, and separating the sodium uranyl acetate from the solution.

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

DTIC Science & Technology

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

Recuperation of uranyl ions from effluents by means of microbiological collectors

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

Cecal, A.; Palamaru, I.; Humelnicu, D.

1997-12-31

This paper deals with the study of bioaccumulation of uranyl ions (UO{sub 2}{sup 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{sub 2}{sup 2+} on the biomass, for several experimental conditions, were established between 14.22 and 91.99%.

Patch testing with uranyl acetate in veterans exposed to depleted uranium during the 1991 Gulf war and the Iraqi conflict.

PubMed

Shvartsbeyn, Marianna; Tuchinda, Papapit; Gaitens, Joanna; Squibb, Katherine S; McDiarmid, Melissa A; Gaspari, Anthony A

2011-01-01

The Depleted Uranium Follow-Up Program is a clinical surveillance program run by the Baltimore Veterans Affairs Medical Center since 1993 for veterans of the Gulf and Iraqi wars who were exposed to depleted uranium (DU) as a result of "friendly-fire" incidents. In 2009, 40 veterans from this cohort were screened for skin reactivity to metals by patch-testing with extended metal series and uranyl acetate (0.25%, 2.5%, and 25%). A control arm comprised 46 patients without any known occupational exposures to DU who were seen at the University of Maryland Dermatology Clinic for evaluation of allergic contact dermatitis. Excluding irritant reactions, no patch-test reactions to uranyl acetate were observed in the participants. Irritant reactions to DU were more common in the clinic cohort, likely reflective of the demographic differences between the two arms of the study. Biologic monitoring of urine uranium concentrations in the DU program participants with 24-hour urine samples showed evidence of percutaneous uranium absorption from the skin patches. We conclude that dermatitis observed in a subset of the veterans was unrelated to their military DU exposure. Our data suggest that future studies of skin testing with uranyl acetate should utilize 0.25%, the least irritating concentration.

KINETICS OF THE DISSOLUTION OF URANIUM DIOXIDE IN CARBONATE-BICARBONATE SOLUTIONS

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

Schortmann, W.E.; DeSesa, M.A.

The kinetics of the dissolution of uranium dioxide in sodium carbonate- sodium bicarbonate solutions were determined. The study was undertaken in order to obtain fundamental information about the commercial carbonate process for leaching uranium from its ores. A rate equation incorporating the effects of surface area oxygen partial pressure, temperature, and reagent concentrations was empirically developed. A mechanism consisting essentially of two consecutive reactions at steady state is proposed. These reactions are the oxidation of U/ sup 4+/ to U/sup 6+/ and the subsequent formation of the uranyl dicarbonate complexion. Depending on the conditions, either or both of these reactionsmore » can determine the over-all rate. The conversion of uranyl dicarbonate to the uranyl tricarbonate complexion is postulated to be very rapid. In the suggested mechanism, the rate-determining phase of the oxidation is the dissociation of adsorbed molecular oxygen. and both the carbonate and bicarbonate ions play equivalent roles in the formation of the uranyl dicarbonate. As indicated by their high activation energies of about 13 and 14 kcal per mole uranium, both reactions are chemical rather than diffusional processes. A mathematical examination of the proposed mechanism produced a rate equation consistent with the experimental information. The credibility of the mechanism was thereby strengthened. (auth)« less

Cellular distribution of uranium after acute exposure of renal epithelial cells: SEM, TEM and nuclear microscopy analysis

NASA Astrophysics Data System (ADS)

Carrière, Marie; Gouget, Barbara; Gallien, Jean-Paul; Avoscan, Laure; Gobin, Renée; Verbavatz, Jean-Marc; Khodja, Hicham

2005-04-01

The major health effect of uranium exposure has been reported to be chemical kidney toxicity, functional and histological damages being mainly observed in proximal tubule cells. Uranium enters the proximal tubule as uranyl-bicarbonate or uranyl-citrate complexes. The aim of our research is to investigate the mechanisms of uranium toxicity, intracellular accumulation and repartition after acute intoxication of rat renal proximal tubule epithelial cells, as a function of its chemical form. Microscopic observations of renal epithelial cells after acute exposure to uranyl-bicarbonate showing the presence of intracellular precipitates as thin needles of uranyl-phosphate localized in cell lysosomes have been published. However the initial site of precipitates formation has not been identified yet: they could either be formed outside the cells before internalization, or directly inside the cells. Uranium solubility as a function and initial concentration was specified by ICP-MS analysis of culture media. In parallel, uranium uptake and distribution in cell monolayers exposed to U-bicarbonate was investigated by nuclear microprobe analyses. Finally, the presence of uranium precipitates was tested out by scanning electron microscopic observations (SEM), while extracellular and/or intracellular precipitates were observed on thin sections of cells by transmission electron microscopy (TEM).

Uranium: A Dentist's perspective

PubMed Central

Toor, R. S. S.; Brar, G. S.

2012-01-01

Uranium is a naturally occurring radionuclide found in granite and other mineral deposits. In its natural state, it consists of three isotopes (U-234, U-235 and U-238). On an average, 1% – 2% of ingested uranium is absorbed in the gastrointestinal tract in adults. The absorbed uranium rapidly enters the bloodstream and forms a diffusible ionic uranyl hydrogen carbonate complex (UO2HCO3+) which is in equilibrium with a nondiffusible uranyl albumin complex. In the skeleton, the uranyl ion replaces calcium in the hydroxyapatite complex of the bone crystal. Although in North India, there is a risk of radiological toxicity from orally ingested natural uranium, the principal health effects are chemical toxicity. The skeleton and kidney are the primary sites of uranium accumulation. Acute high dose of uranyl nitrate delays tooth eruption, and mandibular growth and development, probably due to its effect on target cells. Based on all previous research and recommendations, the role of a dentist is to educate the masses about the adverse effects of uranium on the overall as well as the dental health. The authors recommended that apart from the discontinuation of the addition of uranium to porcelain, the Public community water supplies must also comply with the Environmental Protection Agency (EPA) standards of uranium levels being not more than 30 ppb (parts per billion). PMID:24478959

Impact of uranyl-calcium-carbonato complexes on uranium(VI) adsorption to synthetic and natural sediments.

PubMed

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.

Validation of gamma-ray detection techniques for safeguards monitoring at natural uranium conversion facilities

NASA Astrophysics Data System (ADS)

Dewji, S. A.; Lee, D. L.; Croft, S.; Hertel, N. E.; Chapman, J. A.; McElroy, R. D.; Cleveland, S.

2016-07-01

Recent IAEA circulars and policy papers have sought to implement safeguards when any purified aqueous uranium solution or uranium oxides suitable for isotopic enrichment or fuel fabrication exists. Under the revised policy, IAEA Policy Paper 18, the starting point for nuclear material under safeguards was reinterpreted, suggesting that purified uranium compounds should be subject to safeguards procedures no later than the first point in the conversion process. In response to this technical need, a combination of simulation models and experimental measurements were employed to develop and validate concepts of nondestructive assay monitoring systems in a natural uranium conversion plant (NUCP). In particular, uranyl nitrate (UO2(NO3)2) solution exiting solvent extraction was identified as a key measurement point (KMP), where gamma-ray spectroscopy was selected as the process monitoring tool. The Uranyl Nitrate Calibration Loop Equipment (UNCLE) facility at Oak Ridge National Laboratory was employed to simulate the full-scale operating conditions of a purified uranium-bearing aqueous stream exiting the solvent extraction process in an NUCP. Nondestructive assay techniques using gamma-ray spectroscopy were evaluated to determine their viability as a technical means for drawing safeguards conclusions at NUCPs, and if the IAEA detection requirements of 1 significant quantity (SQ) can be met in a timely way. This work investigated gamma-ray signatures of uranyl nitrate circulating in the UNCLE facility and evaluated various gamma-ray detector sensitivities to uranyl nitrate. These detector validation activities include assessing detector responses to the uranyl nitrate gamma-ray signatures for spectrometers based on sodium iodide, lanthanum bromide, and high-purity germanium detectors. The results of measurements under static and dynamic operating conditions at concentrations ranging from 10-90 g U/L of natural uranyl nitrate are presented. A range of gamma-ray lines is examined, including attenuation for transmission measurement of density and concentration. It was determined that transmission-corrected gamma-ray spectra provide a reliable way to monitor the 235U concentration of uranyl nitrate solution in transfer pipes in NUCPs. Furthermore, existing predictive and analysis methods are adequate to design and realize practical designs. The 137Cs transmission source employed in this work is viable but not optimal for 235U densitometry determination. Validated simulations assessed the viability of 133Ba and 57Co as alternative densitometry sources. All three gamma-ray detectors are viable for monitoring natural uranium feed; although high-purity germanium is easiest to interpret, it is, however, the least attractive as an installation instrument. Overall, for monitoring throughput in a facility such as UNCLE, emulating the uranium concentration and pump speeds of the Springfields conversion facility in the United Kingdom, an uncertainty of less than 0.17% is required in order to detect the diversion of 1 SQ of uranyl nitrate through changes in uranium concentration over an accountancy period of one year with a detection probability of 50%. Although calibrated gamma-ray detection systems are capable of determining the concentration of uranium content in NUCPs, it is only in combination with verifiable operator declarations and supporting data, such as flow rate and enrichment, that safeguards conclusions can be drawn.

Method for photochemical reduction of uranyl nitrate by tri-N-butyl phosphate and application of this method to nuclear fuel reprocessing

DOEpatents

De Poorter, Gerald L.; Rofer-De Poorter, Cheryl K.

1978-01-01

Uranyl ion in solution in tri-n-butyl phosphate is readily photochemically reduced to U(IV). The product U(IV) may effectively be used in the Purex process for treating spent nuclear fuels to reduce Pu(IV) to Pu(III). The Pu(III) is readily separated from uranium in solution in the tri-n-butyl phosphate by an aqueous strip.

Uranyl mediated photofootprinting reveals strong E. coli RNA polymerase--DNA backbone contacts in the +10 region of the DeoP1 promoter open complex.

PubMed Central

Jeppesen, C; Nielsen, P E

1989-01-01

Employing a newly developed uranyl photofootprinting technique (Nielsen et al. (1988) FEBS Lett. 235, 122), we have analyzed the structure of the E. coli RNA polymerase deoP1 promoter open complex. The results show strong polymerase DNA backbone contacts in the -40, -10, and most notably in the +10 region. These results suggest that unwinding of the -12 to +3 region of the promoter in the open complex is mediated through polymerase DNA backbone contacts on both sides of this region. The pattern of bases that are hyperreactive towards KMnO4 or uranyl within the -12 to +3 region furthermore argues against a model in which this region is simply unwound and/or single stranded. The results indicate specific protein contacts and/or a fixed DNA conformation within the -12 to +3 region. Images PMID:2503811

Synthesis of microspheres of triuranium octaoxide by simultaneous water and nitrate extraction from ascorbate-uranyl sols.

PubMed

Brykala, M; Deptula, A; Rogowski, M; Lada, W; Olczak, T; Wawszczak, D; Smolinski, T; Wojtowicz, P; Modolo, G

A new method for synthesis of uranium oxide microspheres (diameter <100 μm) has been developed. It is a variant of our patented Complex Sol-Gel Process, which has been used to synthesize high-quality powders of a wide variety of complex oxides. Starting uranyl-nitrate-ascorbate sols were prepared by addition of ascorbic acid to uranyl nitrate hexahydrate solution and alkalizing by aqueous ammonium hydroxide and then emulsified in 2-ethylhexanol-1 containing 1v/o SPAN-80. Drops of emulsion were firstly gelled by extraction of water by the solvent. Destruction of the microspheres during thermal treatment, owing to highly reactive components in the gels, requires modification of the gelation step by Double Extraction Process-simultaneously extraction of water and nitrates using Primene JMT, which completely eliminates these problem. Final step was calcination in air of obtained microspheres of gels to triuranium octaoxide.

Study of Pulsed Columns with the System. Uranyl Nitrate-Nitric Acid-Water- Tributylphosphate; ETUDE DES COLONNES A PULSATIONS A L'AIDE DU SYSTEME NITRATE D'URANYLE-ACIDE NITRIQUEEAU-TRIBUTYLPHOSPHATE

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

Durandet, J.; Defives, D.; Choffe, B.

1959-10-31

The performsnce of a pulsed column with perforated plates was studied with the aid of a uranyl nitrate-nitric acid --water --tributyl phosphate system. The extraction of uranium from an aqueous acidic solution by an organic solvent and the extraction of uranium from organic solutions by water were the two cases investigated. The variation of the efficiency and the capacity of the pulsed column was determined as a function of the pulse amplitude and frequency, of the total flow rate, of the diameter of the holes, and of the choice of dispersed phase. The results showed that for a given amplitudemore » and total flow rate the efficiency has a maximum with an increase in frequency. (J.S.R.)« less

Thermal stability of uranyl complexes with neutral oxygen-containing organic bases

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

Kobets, L.V.

1987-03-01

The thermal stability of uranyl chloride, nitrate, and oxalate with a series of neutral oxygen-containing organic ligands is discussed. It was found that the temperatures of removal of chlorine are higher than the stripping of the first molecule of the base in complexes UO/sub 2/Cl/sub 2/ x 2L. This is an indication of greater strength of the bonds of the Cl/sup -/ ions to the uranyl group in comparison with the investigated bases. It was shown that the temperatures of removal of a mole of neutral ligands depend little on the nature of the anions and exhibit a correlation withmore » the donor capacity of the bases: Ac < TBP < DMFA similarly ordered DMSO < TBPO similarly ordered PyO. The chemistry of the decomposition of the complexes and the strength of the binding of the acido- and neutral ligands in them are discussed.« less

Topologically and geometrically flexible structural units in seven new organically templated uranyl selenates and selenite–selenates

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

Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru; Kovrugin, Vadim M.; Tyumentseva, Olga S.

2015-09-15

Single crystals of seven novel uranyl oxysalts of selenium with protonated methylamine molecules, [C{sub 2}H{sub 8}N]{sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)] (I), [C{sub 2}H{sub 8}N]{sub 2}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}(H{sub 2}O)] (II), [C{sub 4}H{sub 15}N{sub 3}][H{sub 3}O]{sub 0.5}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 2.93}(SeO{sub 3}){sub 0.07}(H{sub 2}O)](NO{sub 3}){sub 0.5} (III), [C{sub 2}H{sub 8}N]{sub 3}[H{sub 5}O{sub 2}][(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}(H{sub 2}O){sub 2}]{sub 2}(H{sub 2}O){sub 5} (IV), [C{sub 2}H{sub 8}N]{sub 2}[H{sub 3}O][(UO{sub 2}){sub 3}(SeO{sub 4}){sub 4}(HSeO{sub 3})(H{sub 2}O)](H{sub 2}SeO{sub 3}){sub 0.2} (V), [C{sub 4}H{sub 12}N]{sub 3}[H{sub 3}O][(UO{sub 2}){sub 3}(SeO{sub 4}){sub 5}(H{sub 2}O)] (VI), and [C{sub 2}H{sub 8}N]{sub 3}(C{sub 2}H{sub 7}N)[(UO{sub 2}){sub 3}(SeO{sub 4}){submore » 4}(HSeO{sub 3})(H{sub 2}O)] (VII) have been prepared by isothermal evaporation from aqueous solutions. Their crystal structures have been solved by direct methods and their uranyl selenate and selenite–selenate units investigated using black-and-white graphs from the viewpoints of topology of interpolyhedral linkages and isomeric variations. The crystal structure of IV is based upon complex layers with unique topology, which has not been observed previously in uranyl selenates. Investigations of the statistics and local distribution of the U–O{sub br}–Se bond angles demonstrates that shorter angles associate with undulations, whereas larger angles correspond to planar areas of the uranyl selenite layers. - Graphical abstract: Crystal structures of the seven novel Se-contaning uranyl oxysalts that contain protonated organic molecules as interlayer species have been investigated from the viewpoints of topology of interpolyhedral linkages, isomeric variations and flexibility of structural units. - Highlights: • Single crystals of seven novel uranyl oxysalts were prepared by evaporation method. • The graph theory was used for investigation of topologies of structural units. • The method of orientation matrices was applied to distinguish geometrical isomers. • The flexibility of structural complexes specifies the undulation of layered structural units.« less

Neptunium incorporation into select uranyl phases and thermal analysis of select uranyl phases

NASA Astrophysics Data System (ADS)

Klingensmith, Amanda Leigh

Alteration of spent nuclear fuel in a geological repository under oxidizing conditions is likely to result in abundant uranyl compounds. The proposed repository at Yucca Mountain, Nevada is intended to store about 70,000 metric tons of spent nuclear fuel in the unsaturated zone of a welded tuff sequence. Following failure of canisters that encapsulate the waste, contents may be exposed both to air and water and undergo repetitive wetting and drying events. Incorporation of radionuclides into the uranyl alteration phases may significantly reduce their mobility, thereby impacting repository performance. Of particular interest is 237Np owing to its long half-life (2.14 x 106 years) and potential mobility in groundwater. Powders of the synthetic uranyl phase soddyite, (UO2) 2(SiO4)(H2O)2, a framework type structure, and uranophane, Ca[(UO2)(SiO3OH)]2(H 2O)5, kasolite, Pb[(UO2)(SiO4)]H 2O, Na compreignacite, Na2[(UO2)3O 2(OH)3]2(H2O)7, and becquerelite, Ca[(UO2)3O2(OH)3]2(H 2O)8, all of which are sheet type structures, were synthesized in the presence of Np5+ under varying temperature and pH conditions. Uranophane, kasolite, boltwoodite K[(UO2)(SiO3OH)](H 2O)1.5, and Na boltwoodite K,Na[(UO2)(SiO 3OH)](H2O)1.5 were synthesized in the presence of Np as well as P, Ca and/or Mg. Single crystals of Na metaschoepite, Na[(UO 2)4O2(OH)5]˙5H2O were synthesized in the presence of Np5+ and laser ablation verified that Np can be incorporated within the structure of a uranyl phase. Incorporation of Np5+ into soddyite increased steadily with synthesis temperature. Np incorporation into uranophane, becquerelite, and kasolite was not dependent on synthesis temperature. Np uptake in uranophane and kasolite was found to be dependent on synthesis pH, with an increase in Np uptake with higher pH. Uranophane, boltwoodite and Na boltwoodite showed an increase in Np incorporation in the presence of P. Boltwoodite showed an even higher Np uptake when Mg and P were both present in the synthesis. Thermal analysis was completed for the uranyl phases soddyite, becquerelite, Na compreignacite, uranophane, and kasolite. TGA curves for becquerelite, Na compreignacite and uranophane showed loss of interlayer water groups by 100°C. Soddyite and kasolite showed more gradual TGA curves and retention of water groups up to 400°C for soddyite and 550°C for kasolite, with agreement shown by high temperature powder XRD data.

Response to the comment “Uranyl-chloride speciation and uranium transport in hydrothermal brines: Comment on Migdisov et al. (2018)” by Dargent et al.

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

Migdisov, A. A.; Runde, W.; Williams-Jones, A. E.

We welcome the comments provided by Dargent et al. (2018) and appreciate the effort they have made to evaluate our recently reported data on the stability of uranyl(VI) chloride complexes as function of temperature (Migdisov et al., 2018). We also appreciate the opportunity provided by the editor to clarify issues in our paper that were not clearly articulated or in error.

A roadmap to uranium ionic liquids: anti-crystal engineering.

PubMed

Yaprak, Damla; Spielberg, Eike T; Bäcker, Tobias; Richter, Mark; Mallick, Bert; Klein, Axel; Mudring, Anja-Verena

2014-05-19

In the search for uranium-based ionic liquids, tris(N,N-dialkyldithiocarbamato)uranylates have been synthesized as salts of the 1-butyl-3-methylimidazolium (C4mim) cation. As dithiocarbamate ligands binding to the UO2(2+) unit, tetra-, penta-, hexa-, and heptamethylenedithiocarbamates, N,N-diethyldithiocarbamate, N-methyl-N-propyldithiocarbamate, N-ethyl-N-propyldithiocarbamate, and N-methyl-N-butyldithiocarbamate have been explored. X-ray single-crystal diffraction allowed unambiguous structural characterization of all compounds except N-methyl-N-butyldithiocarbamate, which is obtained as a glassy material only. In addition, powder X-ray diffraction as well as vibrational and UV/Vis spectroscopy, supported by computational methods, were used to characterize the products. Differential scanning calorimetry was employed to investigate the phase-transition behavior depending on the N,N-dialkyldithiocarbamato ligand with the aim to establish structure-property relationships regarding the ionic liquid formation capability. Compounds with the least symmetric N,N-dialkyldithiocarbamato ligand and hence the least symmetric anions, tris(N-methyl-N-propyldithiocarbamato)uranylate, tris(N-ethyl-N-propyldithiocarbamato)uranylate, and tris(N-methyl-N-butyldithiocarbamato)uranylate, lead to the formation of (room-temperature) ionic liquids, which confirms that low-symmetry ions are indeed suitable to suppress crystallization. These materials combine low melting points, stable complex formation, and hydrophobicity and are therefore excellent candidates for nuclear fuel purification and recovery. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of vibration frequencies of uranyl ion in complexes with neutral bases (in Russian)

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

Kobets, L.V.; Umreiko, D.S.

1986-12-01

It has been shown that any estimate of the changes in vibration frequencies of UO/sub 2//sup 2 +/ applies only to the series of isostructural compounds with similar stoichiometry. Either the same values of stretching vibration frequencies of uranyl correspond to complexes with ligands that have different donor abilities, or changes in these frequencies are not great and do not reflect the real increase in the donor ability of the bases with respect to proton-containing acceptors. When the acido ligands are replaced or the stoichiometry of the complexes is changed, no correlations can be carried out, since, besides the basicitiesmore » of donors, other parameters such as the dentateness of the ligand, and hence the symmetry and the structure of the compound, are also varied. In this paper, the authors evaluate the contributions of the ligands to the shift of the vibration frequencies of uranyl that have been made and do not take into account the characteristic features of the compounds which therefore led to very different values of the contributions for one and the same ligand in different compounds. To evaluate the shifts produced by the ligands, the value of 1065 cm/sup -1/ was taken as the vibration frequency of a hypothetical fee uranyl ion, not perturbed by bonds with equatorial ligands. The authors also evaluate the contributions of ions able to form polymer structures.« less

Impact of uranyl-calcium-carbonato complexes on uranium(VI) adsorption to synthetic and natural sediments

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

Stewart, B.D.; Mayes, Melanie; Fendorf, Scott

2010-01-01

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 rangemore » of aqueous uranyl species. U(VI) adsorption is directly linked to UO{sub 2}{sup 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{sub d} values decrease from 48 to 17 L kg{sup -1} for goethite, from 64 to 29 L kg{sup -1} for Hanford sediments, and from 95 to 51 L kg{sup -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 ({approx}5) and limited dissolved calcium are optimal for uranium adsorption.« less

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

van Veelen, Arjen; Bargar, John R.; Law, Gareth T. W.

Polarization-dependent grazing incidence X-ray absorption spectroscopy (XAS) measurements were completed on oriented single crystals of magnesite [MgCO 3] and brucite [Mg(OH) 2] reacted with aqueous uranyl chloride above and below the solubility boundaries of schoepite (500, 50, and 5 ppm) at pH 8.3 and at ambient (P CO2 = 10 –3.5) or reduced partial pressures of carbon dioxide (P CO2 = 10 –4.5). X-ray absorption near edge structure (XANES) spectra show a striking polarization dependence (χ = 0° and 90° relative to the polarization plane of the incident beam) and consistently demonstrated that the uranyl molecule was preferentially oriented withmore » its O axial = U(VI) = O axial linkage at high angles (60–80°) to both magnesite (101¯4) and brucite (0001). Extended X-ray absorption fine structure (EXAFS) analysis shows that the “effective” number of U(VI) axial oxygens is the most strongly affected fitting parameter as a function of polarization. Furthermore, axial tilt in the surface thin films (thickness ~ 21 Å) is correlated with surface roughness [σ]. Our results show that hydrated uranyl(-carbonate) complexes polymerize on all of our experimental surfaces and that this process is controlled by surface hydroxylation. Lastly, these results provide new insights into the bonding configuration expected for uranyl complexes on the environmentally significant carbonate and hydroxide mineral surfaces.« less

Uranium immobilization and nanofilm formation on magnesium-rich minerals

DOE PAGES

van Veelen, Arjen; Bargar, John R.; Law, Gareth T. W.; ...

2016-03-18

Polarization-dependent grazing incidence X-ray absorption spectroscopy (XAS) measurements were completed on oriented single crystals of magnesite [MgCO 3] and brucite [Mg(OH) 2] reacted with aqueous uranyl chloride above and below the solubility boundaries of schoepite (500, 50, and 5 ppm) at pH 8.3 and at ambient (P CO2 = 10 –3.5) or reduced partial pressures of carbon dioxide (P CO2 = 10 –4.5). X-ray absorption near edge structure (XANES) spectra show a striking polarization dependence (χ = 0° and 90° relative to the polarization plane of the incident beam) and consistently demonstrated that the uranyl molecule was preferentially oriented withmore » its O axial = U(VI) = O axial linkage at high angles (60–80°) to both magnesite (101¯4) and brucite (0001). Extended X-ray absorption fine structure (EXAFS) analysis shows that the “effective” number of U(VI) axial oxygens is the most strongly affected fitting parameter as a function of polarization. Furthermore, axial tilt in the surface thin films (thickness ~ 21 Å) is correlated with surface roughness [σ]. Our results show that hydrated uranyl(-carbonate) complexes polymerize on all of our experimental surfaces and that this process is controlled by surface hydroxylation. Lastly, these results provide new insights into the bonding configuration expected for uranyl complexes on the environmentally significant carbonate and hydroxide mineral surfaces.« less

Uranium Immobilization and Nanofilm Formation on Magnesium-Rich Minerals.

PubMed

van Veelen, Arjen; Bargar, John R; Law, Gareth T W; Brown, Gordon E; Wogelius, Roy A

2016-04-05

Polarization-dependent grazing incidence X-ray absorption spectroscopy (XAS) measurements were completed on oriented single crystals of magnesite [MgCO3] and brucite [Mg(OH)2] reacted with aqueous uranyl chloride above and below the solubility boundaries of schoepite (500, 50, and 5 ppm) at pH 8.3 and at ambient (PCO2 = 10(-3.5)) or reduced partial pressures of carbon dioxide (PCO2 = 10(-4.5)). X-ray absorption near edge structure (XANES) spectra show a striking polarization dependence (χ = 0° and 90° relative to the polarization plane of the incident beam) and consistently demonstrated that the uranyl molecule was preferentially oriented with its Oaxial═U(VI)═Oaxial linkage at high angles (60-80°) to both magnesite (101̅4) and brucite (0001). Extended X-ray absorption fine structure (EXAFS) analysis shows that the "effective" number of U(VI) axial oxygens is the most strongly affected fitting parameter as a function of polarization. Furthermore, axial tilt in the surface thin films (thickness ∼ 21 Å) is correlated with surface roughness [σ]. Our results show that hydrated uranyl(-carbonate) complexes polymerize on all of our experimental surfaces and that this process is controlled by surface hydroxylation. These results provide new insights into the bonding configuration expected for uranyl complexes on the environmentally significant carbonate and hydroxide mineral surfaces.

A roadmap to uranium ionic liquids: Anti-crystal engineering

DOE PAGES

Yaprak, Damla; Spielberg, Eike T.; Bäcker, Tobias; ...

2014-04-15

In the search for uranium-based ionic liquids, tris(N,N-dialkyldithiocarbamato)uranylates have been synthesized as salts of the 1-butyl-3-methylimidazolium (C 4mim) cation. As dithiocarbamate ligands binding to the UO 2 2+ unit, tetra-, penta-, hexa-, and heptamethylenedithiocarbamates, N,N-diethyldithiocarbamate, N-methyl-N-propyldithiocarbamate, N-ethyl-N-propyldithiocarbamate, and N-methyl-N-butyldithiocarbamate have been explored. X-ray single-crystal diffraction allowed unambiguous structural characterization of all compounds except N-methyl-N-butyldithiocarbamate, which is obtained as a glassy material only. In addition, powder X-ray diffraction as well as vibrational and UV/Vis spectroscopy, supported by computational methods, were used to characterize the products. Differential scanning calorimetry was employed to investigate the phase-transition behavior depending on the N,N-dialkyldithiocarbamato ligand withmore » the aim to establish structure–property relationships regarding the ionic liquid formation capability. Compounds with the least symmetric N,N-dialkyldithiocarbamato ligand and hence the least symmetric anions, tris(N-methyl-N-propyldithiocarbamato)uranylate, tris(N-ethyl-N-propyldithiocarbamato)uranylate, and tris(N-methyl-N-butyldithiocarbamato)uranylate, lead to the formation of (room-temperature) ionic liquids, which confirms that low-symmetry ions are indeed suitable to suppress crystallization. As a result, these materials combine low melting points, stable complex formation, and hydrophobicity and are therefore excellent candidates for nuclear fuel purification and recovery.« less

Validation of gamma-ray detection techniques for safeguards monitoring at natural uranium conversion facilities

DOE PAGES

Dewji, Shaheen A.; Lee, Denise L.; Croft, Stephen; ...

2016-03-28

Recent IAEA circulars and policy papers have sought to implement safeguards when any purified aqueous uranium solution or uranium oxides suitable for isotopic enrichment or fuel fabrication exists. Under the revised policy, IAEA Policy Paper 18, the starting point for nuclear material under safeguards was reinterpreted, suggesting that purified uranium compounds should be subject to safeguards procedures no later than the first point in the conversion process. In response to this technical need, a combination of simulation models and experimental measurements were employed to develop and validate concepts of nondestructive assay monitoring systems in a natural uranium conversion plant (NUCP).more » In particular, uranyl nitrate (UO 2(NO 3) 2) solution exiting solvent extraction was identified as a key measurement point (KMP), where gamma-ray spectroscopy was selected as the process monitoring tool. The Uranyl Nitrate Calibration Loop Equipment (UNCLE) facility at Oak Ridge National Laboratory was employed to simulate the full-scale operating conditions of a purified uranium-bearing aqueous stream exiting the solvent extraction process in an NUCP. Nondestructive assay techniques using gamma-ray spectroscopy were evaluated to determine their viability as a technical means for drawing safeguards conclusions at NUCPs, and if the IAEA detection requirements of 1 significant quantity (SQ) can be met in a timely way. This work investigated gamma-ray signatures of uranyl nitrate circulating in the UNCLE facility and evaluated various gamma-ray detector sensitivities to uranyl nitrate. These detector validation activities include assessing detector responses to the uranyl nitrate gamma-ray signatures for spectrometers based on sodium iodide, lanthanum bromide, and high-purity germanium detectors. The results of measurements under static and dynamic operating conditions at concentrations ranging from 10–90 g U/L of natural uranyl nitrate are presented. A range of gamma-ray lines is examined, including attenuation for transmission measurement of density and concentration. It was determined that transmission-corrected gamma-ray spectra provide a reliable way to monitor the 235U concentration of uranyl nitrate solution in transfer pipes in NUCPs. Furthermore, existing predictive and analysis methods are adequate to design and realize practical designs. The 137Cs transmission source employed in this work is viable but not optimal for 235U densitometry determination. Validated simulations assessed the viability of 133Ba and 57Co as alternative densitometry sources. All three gamma-ray detectors are viable for monitoring natural uranium feed; although high-purity germanium is easiest to interpret, it is, however, the least attractive as an installation instrument. Overall, for monitoring throughput in a facility such as UNCLE, emulating the uranium concentration and pump speeds of the Springfields conversion facility in the United Kingdom, an uncertainty of less than 0.17% is required in order to detect the diversion of 1 SQ of uranyl nitrate through changes in uranium concentration over an accountancy period of one year with a detection probability of 50%. As a result, calibrated gamma-ray detection systems are capable of determining the concentration of uranium content in NUCPs, it is only in combination with verifiable operator declarations and supporting data, such as flow rate and enrichment, that safeguards conclusions can be drawn.« less

Molecular-scale characterization of uranium sorption by bone apatite materials for a permeable reactive barrier demonstration

USGS Publications Warehouse

Fuller, C.C.; Bargar, J.R.; Davis, J.A.

2003-01-01

Uranium binding to bone charcoal and bone meal apatite materials was investigated using U LIII-edge EXAFS spectroscopy and synchrotron source XRD measurements of laboratory batch preparations in the absence and presence of dissolved carbonate. Pelletized bone char apatite recovered from a permeable reactive barrier (PRB) at Fry Canyon, UT, was also studied. EXAFS analyses indicate that U(VI) sorption in the absence of dissolved carbonate occurred by surface complexation of U(VI) for sorbed concentrations ??? 5500 ??g U(VI)/g for all materials with the exception of crushed bone char pellets. Either a split or a disordered equatorial oxygen shell was observed, consistent with complexation of uranyl by the apatite surface. A second shell of atoms at a distance of 2.9 A?? was required to fit the spectra of samples prepared in the presence of dissolved carbonate (4.8 mM total) and is interpreted as formation of ternary carbonate complexes with sorbed U(VI). A U-P distance at 3.5-3.6 A?? was found for most samples under conditions where uranyl phosphate phases did not form, which is consistent with monodentate coordination of uranyl by phosphate groups in the apatite surface. At sorbed concentrations ??? 5500 ??g U(VI)/g in the absence of dissolved carbonate, formation of the uranyl phosphate solid phase, chernikovite, was observed. The presence of dissolved carbonate (4.8 mM total) suppressed the formation of chernikovite, which was not detected even with sorbed U(VI) up to 12 300 ??g U(VI)/g in batch samples of bone meal, bone charcoal, and reagent-grade hydroxyapatite. EXAFS spectra of bone char samples recovered from the Fry Canyon PRB were comparable to laboratory samples in the presence of dissolved carbonate where U(VI) sorption occurred by surface complexation. Our findings demonstrate that uranium uptake by bone apatite will probably occur by surface complexation instead of precipitation of uranyl phosphate phases under the groundwater conditions found at many U-contaminated sites.

GRAPHITE PRODUCTION UTILIZING URANYL NITRATE HEXAHYDRATE CATALYST

DOEpatents

Sheinberg, H.; Armstrong, J.R.; Schell, D.H.

1964-03-10

ABS>The graphitizing of a mixture composed of furfuryl alcohol binder and uranyl nitrate hexahydrate hardener and the subsequent curing, baking, and graphitizing with pressure being initially applied prior to curing are described. The pressure step may be carried out by extrusion, methyl cellulose being added to the mixture before the completion of extrusion. Uranium oxide may be added to the graphitizable mixture prior to the heating and pressure steps. The graphitizable mixture may consist of discrete layers of different compositions. (AEC)

Method of precipitating uranium from an aqueous solution and/or sediment

DOEpatents

Tokunaga, Tetsu K; Kim, Yongman; Wan, Jiamin

2013-08-20

A method for precipitating uranium from an aqueous solution and/or sediment comprising uranium and/or vanadium is presented. The method includes precipitating uranium as a uranyl vanadate through mixing an aqueous solution and/or sediment comprising uranium and/or vanadium and a solution comprising a monovalent or divalent cation to form the corresponding cation uranyl vanadate precipitate. The method also provides a pathway for extraction of uranium and vanadium from an aqueous solution and/or sediment.

Carbonate-H2O2 Leaching for Sequestering Uranium from Seawater

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

Pan, Horng-Bin; Weisheng, Liao; Wai, Chien

Uranium adsorbed on amidoxime-based polyethylene fiber in simulated seawater can be quantitatively eluted at room temperature using 1M Na2CO3 containing 0.1 M H2O2. This efficient elution process is probably due to formation of an extremely stable uranyl-peroxo-carbonato complex in the carbonate solution. After washing with water, the sorbent can be reused with little loss of uranium loading capacity. Possible existence of this stable uranyl species in ocean water is also discussed.

Carbonate-H₂O₂ leaching for sequestering uranium from seawater.

PubMed

Pan, Horng-Bin; Liao, Weisheng; Wai, Chien M; Oyola, Yatsandra; Janke, Christopher J; Tian, Guoxin; Rao, Linfeng

2014-07-28

Uranium adsorbed on amidoxime-based polyethylene fiber in simulated seawater can be quantitatively eluted at room temperature using 1 M Na2CO3 containing 0.1 M H2O2. This efficient elution process is probably due to the formation of an extremely stable uranyl-peroxo-carbonato complex in the carbonate solution. After washing with water, the sorbent can be reused with minimal loss of uranium loading capacity. Possible existence of this stable uranyl species in ocean water is also discussed.

SEPARATION OF BARIUM VALUES FROM URANYL NITRATE SOLUTIONS

DOEpatents

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.

URANIUM RECOVERY PROCESS

DOEpatents

Hyman, H.H.; Dreher, J.L.

1959-07-01

The recovery of uranium from the acidic aqueous metal waste solutions resulting from the bismuth phosphate carrier precipitation of plutonium from solutions of neutron irradiated uranium is described. The waste solutions consist of phosphoric acid, sulfuric acid, and uranium as a uranyl salt, together with salts of the fission products normally associated with neutron irradiated uranium. Generally, the process of the invention involves the partial neutralization of the waste solution with sodium hydroxide, followed by conversion of the solution to a pH 11 by mixing therewith sufficient sodium carbonate. The resultant carbonate-complexed waste is contacted with a titanated silica gel and the adsorbent separated from the aqueous medium. The aqueous solution is then mixed with sufficient acetic acid to bring the pH of the aqueous medium to between 4 and 5, whereby sodium uranyl acetate is precipitated. The precipitate is dissolved in nitric acid and the resulting solution preferably provided with salting out agents. Uranyl nitrate is recovered from the solution by extraction with an ether such as diethyl ether.

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

Abrao, Alcidio.; Araujo, Jose Adroaldo de; Franca Junior, J.M.

This paper describes a technique for the production of nuclear grade ammonium diuranate (ADU) using uranyl sulfate solutions obtained as eluate from the ion exchange (strong cationic resin) purification of uranium, by precipitation with NH{sub 3} gas. The precipitation of ADU by direct introduction of NH{sub 3} gas into acid uranyl sulfate solution has as consequence a high coprecipitation of sulfate ion, reaching ratios as high as 10 to 14% SO{sub 4}/ADU. To overcome this serious inconvenience, the reverse order of addition of reagents was studied, the ADU precipitation being done in such a way that the pH of themore » mixture was kept higher than 6 during the whole precipitation. This modification, in conjunction with the adjustment of other precipitation parameters, like temperature, precipitation time, aging time, concentration of uranium in uranyl sulfate and pH, allowed a sucessful precipitation of ADU with low sulfate content. The technique was applied at pilot plant scale, using batch and continuous precipitation, in both cases the obtained ADU was low in sulfate.« less

A novel stable 3D luminescent uranyl complex for highly efficient and sensitive recognition of Ru3+ and biomolecules

NASA Astrophysics Data System (ADS)

Tian, Hong-Hong; Chen, Liang-Ting; Zhang, Rong-Lan; Zhao, Jian-She; Liu, Chi-Yang; Weng, Ng Seik

2018-02-01

A novel highly stable 3D luminescent uranyl coordination polymer, namely {[UO2(L)]·DMA}n (1), was assembled with uranyl salt and a glycine-derivative ligand [6-(carboxymethyl-amino)-4-oxo-4,5-dihydro-[1,3,5]triazin-2-ylamino]-acetic acid (H2L) under solvothermal reaction. Besides, It was found that complex 1 possesses excellent luminescent properties, particularly the efficient selectivity and sensitivity in the recognition of Ru3+, biomacromolecule bovine serum albumin (BSA), biological small molecules dopamine (DA), ascorbic acid (AA) and uric acid (UA) in the water solution based on a "turn-off" mechanism. Accordingly, the luminescent explorations also demonstrated that complex 1 could be acted as an efficient luminescent probe with high quenching efficiency and low detection limit for selectively detecting Ru3+ and biomolecules (DA, AA, UA and BSA). It was noted that the framework structure of complex 1 still remains highly stable after quenching, which was verified by powder X-ray diffraction (PXRD).

Recovery of uranium from an irradiated solid target after removal of molybdenum-99 produced from the irradiated target

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

Reilly, Sean Douglas; May, Iain; Copping, Roy

A process for minimizing waste and maximizing utilization of uranium involves recovering uranium from an irradiated solid target after separating the medical isotope product, molybdenum-99, produced from the irradiated target. The process includes irradiating a solid target comprising uranium to produce fission products comprising molybdenum-99, and thereafter dissolving the target and conditioning the solution to prepare an aqueous nitric acid solution containing irradiated uranium. The acidic solution is then contacted with a solid sorbent whereby molybdenum-99 remains adsorbed to the sorbent for subsequent recovery. The uranium passes through the sorbent. The concentrations of acid and uranium are then adjusted tomore » concentrations suitable for crystallization of uranyl nitrate hydrates. After inducing the crystallization, the uranyl nitrate hydrates are separated from a supernatant. The process results in the purification of uranyl nitrate hydrates from fission products and other contaminants. The uranium is therefore available for reuse, storage, or disposal.« less

Polymorphism in alkali metal uranyl nitrates: Synthesis and crystal structure of gamma-K(UO2)(NO3)3

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

Jouffret, Laurent J.; Krivovichev, Sergey V.; Burns, Peter C.

2011-07-20

Single crystals of γ-K(UO₂)(NO₃)₃ were prepared from aqueous solutions by evaporation. The crystal structure [orthorhombic, Pbca (61), a = 9.2559(3) Å, b = 12.1753(3) Å, c = 15.8076(5) Å, V = 1781.41(9) ų, Z = 8] was determined by direct methods and refined to R₁ = 0.0267 on the basis of 3657 unique observed reflections. The structure is composed of isolated anionic uranyl trinitrate units, [(UO₂)(NO₃)₃] –, that are linked through eleven-coordinated K + cations. Both known polymorphs of K(UO₂)(NO₃)₃ (α- and γ-phases) can be considered as based upon sheets of isolated complex [(UO₂)(NO₃)₃] – ions separated by K +more » cations. The existence of polymorphism in the two K[UO₂(NO₃)₃] polymorphs is due to the different packing modes of uranyl trinitrate clusters that adopt the same two-dimensional but different three-dimensional arrangements.« less

ELECTRON STAINS

PubMed Central

Zobel, C. Richard; Beer, Michael

1961-01-01

Chemical studies have been carried out on the interaction of DNA with uranyl salts. The effect of variations in pH, salt concentration, and structural integrity of the DNA on the stoichiometry of the salt-substrate complex have been investigated. At pH 3.5 DNA interacts with uranyl ions in low concentration yielding a substrate metal ion complex with a UO2++/P mole ratio of about ½ and having a large association constant. At low pH's (about 2.3) the mole ratio decreases to about ⅓. Destruction of the structural integrity of the DNA by heating in HCHO solutions leads to a similar drop in the amount of metal ion bound. Raising the pH above 3.5 leads to an apparent increase in binding as does increasing the concentration of the salt solution. This additional binding has a lower association constant. Under similar conditions DNA binds about seven times more uranyl ion than bovine serum albumin, indicating useful selectivity in staining for electron microscopy. PMID:13788706

Efficient tetracycline adsorption and photocatalytic degradation of rhodamine B by uranyl coordination polymer

NASA Astrophysics Data System (ADS)

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.

A Family of Uranyl Coordination Polymers Containing O-Donor Dicarboxylates and Trispyridyltriazine Guests

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

Thangavelu, Sonia G.; Cahill, Christopher L.

Four uranyl coordination polymers [UO2(C6H8O4)(H2O)2](C18H12N6)2 (1), [UO2(C8H4O4)(H2O)2](C18H12N6)2 (2), Na[(UO2)(C12H6O4)2](C18H13N6)·H2O (3), and Na[(UO2)(C16H8O4)(C6H3NO2)](C18H12N6)·H2O (4) containing aliphatic (adipic acid) or aromatic linkers (1,4-benzene dicarboxylic acid (BDC), 1,4-napthalene dicarboxylic acid (NDC), anthracene 9,10-dicarboxylic acid (ADC)) were synthesized and characterized using single crystal X-ray diffraction, powder X-ray diffraction, and luminescence spectroscopy. The π-stacking distances or the number of π–π interactions present between trispyridyltriazine (TPTZ) guests or the host framework in 1–4 may be affected by the size of the O-donor linker (adipic acid < BDC < NDC < ADC). Luminescence studies show that substitution between adipic acid and BDC influences the emission of 1more » and 2, in which the emission of 1 shows a red shift relative to that of 2. Uranyl emission was not observed in 3 and 4, and may be attributed to the position of the NDC and ADC triplet state relative to the emissive uranyl species.« less

A Family of Uranyl Coordination Polymers Containing O-Donor Dicarboxylates and Trispyridyltriazine Guests

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

Thangavelu, Sonia G.; Cahill, Christopher L.

2016-01-06

Four uranyl coordination polymers [UO2(C6H8O4)(H2O)2](C18H12N6)2 (1), [UO2(C8H4O4)(H2O)2](C18H12N6)2 (2), Na[(UO2)(C12H6O4)2](C18H13N6)·H2O (3), and Na[(UO2)(C16H8O4)(C6H3NO2)](C18H12N6)·H2O (4) containing aliphatic (adipic acid) or aromatic linkers (1,4-benzene dicarboxylic acid (BDC), 1,4-napthalene dicarboxylic acid (NDC), anthracene 9,10-dicarboxylic acid (ADC)) were synthesized and characterized using single crystal X-ray diffraction, powder X-ray diffraction, and luminescence spectroscopy. The π-stacking distances or the number of π–π interactions present between trispyridyltriazine (TPTZ) guests or the host framework in 1–4 may be affected by the size of the O-donor linker (adipic acid < BDC < NDC < ADC). Luminescence studies show that substitution between adipic acid and BDC influences the emission of 1more » and 2, in which the emission of 1 shows a red shift relative to that of 2. Uranyl emission was not observed in 3 and 4, and may be attributed to the position of the NDC and ADC triplet state relative to the emissive uranyl species.« less

Determination of uranyl incorporation into biogenic manganese oxides using X-ray absorption spectroscopy and scattering

USGS Publications Warehouse

Webb, S.M.; Fuller, C.C.; Tebo, B.M.; Bargar, J.R.

2006-01-01

Biogenic manganese oxides are common and an important source of reactive mineral surfaces in the environment that may be potentially enhanced in bioremediation cases to improve natural attenuation. Experiments were performed in which the uranyl ion, UO22+ (U(VI)), at various concentrations was present during manganese oxide biogenesis. At all concentrations, there was strong uptake of U onto the oxides. Synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray diffraction (XRD) studies were carried out to determine the molecular-scale mechanism by which uranyl is incorporated into the oxide and how this incorporation affects the resulting manganese oxide structure and mineralogy. The EXAFS experiments show that at low concentrations (2 mol % U, >4 ??M U(VI) in solution), the presence of U(VI) affects the stability and structure of the Mn oxide to form poorly ordered Mn oxide tunnel structures, similar to todorokite. EXAFS modeling shows that uranyl is present in these oxides predominantly in the tunnels of the Mn oxide structure in a tridentate complex. Observations by XRD corroborate these results. Structural incorporation may lead to more stable U(VI) sequestration that may be suitable for remediation uses. These observations, combined with the very high uptake capacity of the Mn oxides, imply that Mn-oxidizing bacteria may significantly influence dissolved U(VI) concentrations in impacted waters via sorption and incorporation into Mn oxide biominerals. ?? 2006 American Chemical Society.

In situ ligand synthesis with the UO22+ cation under hydrothermal conditions

NASA Astrophysics Data System (ADS)

Frisch, Mark; Cahill, Christopher L.

2007-09-01

A novel uranium (VI) coordination polymer, (UO 2) 2(C 2O 4)(C 5H 6NO 3) 2 ( 1), has been prepared under the hydrothermal reaction of uranium nitrate hexahydrate and L-pyroglutamic acid. Compound 1 (monoclinic, C2/ c, a=22.541(6) Å, b=5.7428(15) Å, c=15.815(4) Å, β=119.112(4)°, Z=4, R1=0.0237, w R2=0.0367) consists of uranium pentagonal bipyramids linked via L-pyroglutamate and oxalate anions to form an overall two-dimensional (2D) structure. With the absence of oxalic acid within the starting materials, the oxalate anions are hypothesized to form in situ whereby decarboxylation of L-pyroglutamic acid occurs followed by coupling of CO 2 to form the oxalate linkages as observed in the crystal structure. Addition of copper (II) to this system appears to promote oxalate formation in that synthetic moolooite (Cu(C 2O 4)· nH 2O; 0⩽ n⩽1) and a known uranyl oxalate [(UO 2) 2(C 2O 4)(OH) 2(H 2O) 2·H 2O], co-crystallize in significant quantity. Compound 1 exhibits the characteristic uranyl emission spectrum upon either direct uranyl excitation or ligand excitation, the latter of which shows an increase in relative intensity. This subsequent increase in the intensity indicates an energy transfer from the ligand to the uranyl cations thus illustrating an example of the antenna effect in the solid state.

Structural evolution of a uranyl peroxide nano-cage fullerene: U60, at elevated pressures

NASA Astrophysics Data System (ADS)

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 that uranyl peroxide nano-cage clusters are persistent once formed, regardless of the state of the cluster: crystalline, amorphous, or in solution. These results add to the body of evidence suggesting that uranyl peroxides are important compounds to consider when dealing with environmental impacts of nuclear waste contamination.

Influence of the Organic Species and Oxoanion in the Synthesis of two Uranyl Sulfate Hydrates, (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 ­(H 2 O)]·7H 2 O and (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 (H 2 O)]·4H 2 O, and a Uranyl Selenate-Selenite [C 5 H 6 N][(UO 2 )(SeO 4 )(HSeO 3 )

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

Jouffret, Laurent J.; Wylie, Ernest M.; Burns, Peter C.

2012-08-08

Two uranyl sulfate hydrates, (H3O)2[(UO2)2(SO4)3(H2O)]·7H2O (NDUS) and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O (NDUS1), and one uranyl selenate-selenite [C5H6N][(UO2)(SeO4)(HSeO3)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L-cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P21/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4)more » Å, β = 112.778(1)°, V = 2153.52(9) Å3,Z = 4, the tetragonal space group P43212, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) Å3, Z = 8, and in the monoclinic space group P21/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) Å3, Z = 4, respectively.The structural units of NDUS and NDUS1 are two-dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two-dimensional uranyl selenate-selenite sheets with a U/Se ratio of 1/2. In-situ reaction of the L-cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H3O+ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C5H6N+ cations result from the cyclization of the carboxyl groups of L-cystine, balancing the charge of the sheets.« less

Experiments on Anion Exchange with Amberlite Ir-120 Resin; ENSAYOS DE INTERCAMBIO ANIONICO CON RESINA AMBERLITA Ir-120

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

Cellini, R.F.; Palomino, J.V.

1956-01-01

The ion exchange of the uranyl ion on Amberlite Ir-120 resin was studied with different uranyl ion concentrations. Elution with sulfuric acid was investlgated and the elution curve for the experimental conditions was determined. From the concentrations of the ions of Cu/sup 2+/, Ni/sup 2+/, Fe/sup 3+/, Cd/sup 2+/, Mn/sup 2+/, and Cr/sup 3+/ the maximum exchange capacity was tested and elation curves with 4 N sulfuric acid were obtained. (tr-auth)

Reductive stripping process for the recovery of uranium from wet-process phosphoric acid

DOEpatents

Hurst, Fred J.; Crouse, David J.

1984-01-01

A reductive stripping flow sheet for recovery of uranium from wet-process phosphoric acid is described. Uranium is stripped from a uranium-loaded organic phase by a redox reaction converting the uranyl to uranous ion. The uranous ion is reoxidized to the uranyl oxidation state to form an aqueous feed solution highly concentrated in uranium. Processing of this feed through a second solvent extraction cycle requires far less stripping reagent as compared to a flow sheet which does not include the reductive stripping reaction.

Optimizing Metalloporphyrin-Catalyzed Reduction Reactions for In Situ Remediation of DOE Contaminants

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

Schlautman, Mark A.

2013-07-14

Past activities have resulted in a legacy of contaminated soil and groundwater at Department of Energy facilities nationwide. Uranium and chromium are among the most frequently encountered and highest-priority metal and radionuclide contaminants at DOE installations. Abiotic chemical reduction of uranium and chromium at contaminated DOE sites can be beneficial because the reduced metal species are less soluble in water, less mobile in the environment, and less toxic to humans and ecosystems. Although direct biological reduction has been reported for U(VI) and Cr(VI) in laboratory studies and at some field sites, the reactions can sometimes be slow or even inhibitedmore » due to unfavorable environmental conditions. One promising approach for the in-situ remediation of DOE contaminants is to develop electron shuttle catalysts that can be delivered precisely to the specific subsurface locations where contaminants reside. Previous research has shown that reduction of oxidized organic and inorganic contaminants often can be catalyzed by electron shuttle systems. Metalloporphyrins and their derivatives are well known electron shuttles for many biogeochemical systems, and thus were selected to study their catalytic capabilities for the reduction of chromium and uranium in the presence of reducing agents. Zero valent iron (ZVI) was chosen as the primary electron donor in most experimental systems. Research proceeded in three phases and the key findings of each phase are reported here. Phase I examined Cr(VI) reduction and utilized micro- and nano-sized ZVI as the electron donors. Electron shuttle catalysts tested were cobalt- and iron-containing metalloporphyrins and Vitamin B12. To aid in the recycle and reuse of the nano-sized ZVI and soluble catalysts, sol-gels and calcium-alginate gel beads were tested as immobilization/support matrices. Although the nano-sized ZVI could be incorporated within the alginate gel beads, preliminary attempts to trap it in sol-gels were not successful. Conversely, the water-soluble catalysts could be trapped within sol-gel matrices but they tended to leach out of the alginate gel beads during use. In general, immobilization of the nano-sized ZVI in gel beads and of the catalysts in sol-gels tended to result in slower rates of Cr(VI) reduction, but these effects could be overcome to some extent by using higher reactant/catalyst concentrations. In addition, the lowering of their effectiveness would likely be offset by the benefits obtained when recycling and reusing the materials because they were immobilized. Addition of the catalytic electron shuttles will be most useful when the micro-sized or nano-sized ZVI becomes less reactive with reaction time. Continued work in Phase II in the area of nano-sized ZVI immobilization led to procedures that were successful in incorporating the iron particles in sol-gel matrices. The water-soluble reductants sodium dithionite and L-ascorbic acid were also tested, but their use appeared to lead to formation of complexes with the uranyl cation which limited their effectiveness. Also, although the sol-gel supported nano-sized ZVI showed some promise at reducing uranium, the fluoride used in the sol-gel synthesis protocol appeared to lead to formation of uranyl-fluoride complexes that were less reactive. Because hexavalent chromium is an anion which does not form complexes with fluoride, it was used to demonstrate the intrinsic reactivity of the sol-gel immobilized nano-sized ZVI. Consistent with our observations in Phase I, the sol-gel matrix once again slowed down the reduction reaction but the expected benefits of recycle/reuse should outweigh this adverse effect. The major emphasis in Phase III of this study was to simultaneously incorporate nano-sized ZVI and water-soluble catalysts in the same sol-gel matrix. The catalysts utilized were cobalt complexes of uroporphyrin and protoporphyrin and Cr(VI) reduction was used to test the efficacy of the combined "catalyst + reductant" sol-gel matrix. When enough catalyst was added to the sol-gels, enhancement of the Cr(VI) reduction reaction was observed. At the lowest levels of catalyst addition, however, the rates of Cr(VI) reduction were similar to those systems which only used sol-gel immobilized nano-sized ZVI without any catalyst present. These findings suggest future areas of research that should be pursued to further optimize abiotic reduction reactions of metals with combined "catalyst + reductant" matrices.« less

Amine templating effect absent in uranyl sulfates synthesized with 1,4-n-butyldiamine

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

Jouffret, Laurent J., E-mail: ljouffret@nd.edu; Wylie, Ernest M.; Burns, Peter C.

2013-01-15

Two new uranyl sulfates, (C{sub 4}H{sub 14}N{sub 2})[(UO{sub 2}){sub 2}(SO{sub 4}){sub 3}(H{sub 2}O)]{center_dot}2H{sub 2}O (NDUS2) and (C{sub 4}H{sub 14}N{sub 2})[(UO{sub 2})(SO{sub 4}){sub 2}(H{sub 2}O)]{center_dot}2H{sub 2}O (NDUS3), were synthesized and their crystal structures determined. NDUS2 was obtained in highly acidic media heat-treated at 373 K and subsequently maintained at 278 K until crystals formed after two months. NDUS3 results from the degradation of NDUS2 over the course of a few days. NDUS2 and NDUS3 crystallize in the monoclinic space group P2{sub 1}/n, a=10.9075(4) A, b=10.4513(4) A, c=17.7881(7) A, {beta}=97.908(2) Degree-Sign , V=2008.52(13) A{sup 3}, Z=4, at 140 K and a=8.8570(4) A,more » b=7.3299(3) A, c=20.4260(9) A, {beta}=95.140(2) Degree-Sign , V=1320.74(10) A{sup 3}, Z=4, at 140 K, respectively. The compounds contain interlayer 1,4-n-butyldiammonium cations that charge-balance the anionic structural units. - Graphical abstract: Amine templating effect absent in uranyl sulfates synthesized with 1,4-diaminobutane, as shown by the synthesis of two new uranyl sulfates, (C{sub 4}H{sub 14}N{sub 2})[(UO{sub 2}){sub 2}(SO{sub 4}){sub 3}(H{sub 2}O)]{center_dot}2H{sub 2}O (NDUS2) and (C{sub 4}H{sub 14}N{sub 2})[(UO{sub 2})(SO{sub 4}){sub 2}(H{sub 2}O)]{center_dot}2H{sub 2}O (NDUS3). Highlights: Black-Right-Pointing-Pointer Two layered uranyl sulfates were synthesized. Black-Right-Pointing-Pointer Amine molecules are located in the interlayers of the compounds. Black-Right-Pointing-Pointer No templating effect of the amine was observed. Black-Right-Pointing-Pointer Amine molecules are only charge balancing cations in the structures.« less

Use of spectroscopic techniques for uranium(VI)/montmorillonite interaction modeling.

PubMed

Kowal-Fouchard, A; Drot, R; Simoni, E; Ehrhardt, J J

2004-03-01

To experimentally identify both clay sorption sites and sorption equilibria and to understand the retention mechanisms at a molecular level, we have characterized the structure of hexavalent uranium surface complexes resulting from the interaction between the uranyl ions and the surface retention groups of a montmorillonite clay. We have performed laser-induced fluorescence spectroscopy (LIFS) and X-ray photoelectron spectroscopy (XPS) on uranyl ion loaded montmorillonite. These structural results were then compared to those obtained from the study of uranyl ions sorbed onto an alumina and also from U(VI) sorbed on an amorphous silica. This experimental approach allowed for a clear determination of the reactive surface sites of montmorillonite for U(VI) sorption. The lifetime values and the U4f XPS spectra of uranium(VI) sorbed on montmorillonite have shown that this ion is sorbed on both exchange and edge sites. The comparison of U(VI)/clay and U(VI)/oxide systems has determined that the interaction between uranyl ions and montmorillonite edge sites occurs via both [triple bond]AlOH and [triple bond]SiOH surface groups and involves three distinct surface complexes. The surface complexation modeling of the U(VI)/montmorillonite sorption edges was determined using the constant capacitance model and the above experimental constraints. The following equilibria were found to account for the uranyl sorption mechanisms onto montmorillonite for metal concentrations ranged from 10(-6) to 10(-3) M and two ionic strengths (0.1 and 0.5 M): 2[triple bond]XNa + UO2(2+) <==> ([triple bond]X)2UO2 + 2Na+, log K0(exch) = 3.0; [triple bond]Al(OH)2 + UO2(2+) <==> [triple bond]Al(OH)2UO2(2+), log K0(Al) = 14.9; [triple bond]Si(OH)2 + UO2(2+) <==> [triple bond]SiO2UO2 + 2H+, log K0(Si1) = -3.8; and [triple bond]Si(OH)2 + 3UO2(2+) + 5H2O <==> [triple bond]SiO2(UO2)3(OH)5- + 7H+, log K0(Si2) = -20.0.

Interfacial Interaction of Titania Nanoparticles and Ligated Uranyl Species: A Relativistic DFT Investigation.

PubMed

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 character of molecular orbitals and energetic order although differing in highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps and orbital energy levels, but changes can be accomplished by adding carbonato and hydroxo ligands.

Structural characterization of environmentally relevant ternary uranyl citrate complexes present in aqueous solutions and solid state materials.

PubMed

Basile, Madeline; Unruh, Daniel K; Flores, Erin; Johns, Adam; Forbes, Tori Z

2015-02-14

Organic acids are important metal chelators in environmental systems and tend to form soluble complexes in aqueous solutions, ultimately influencing the transport and bioavailability of contaminants in surface and subsurface waters. This is particularly true for the formation of uranyl citrate complexes, which have been utilized in advanced photo- and bioremediation strategies for soils contaminated with nuclear materials. Given the complexity of environmental systems, the formation of ternary or heterometallic uranyl species in aqueous solutions are also expected, particularly with Al(iii) and Fe(iii) cations. These ternary forms are reported to be more stable in aqueous solutions, potentially enhancing contaminant mobility and uptake by organisms, but the exact coordination geometries of these soluble molecular complexes have not been elucidated. To provide insight into the nature of these species, we have developed a series of geochemical model compounds ([(UO(2))(2)Al(2)(C(6)H(4)O(7))(4)](6-) (U(2)Al(2)), [(UO(2))(2)Fe(2)(C(6)H(4)O(7))(4)](6-) (U(2)Fe(2)-1) and [(UO(2))(2)Fe(2)(C(6)H(4)O(7))(4)(H(2)O)(2)](6-) (U(2)Fe(2)-2) and [(UO(2))(2)Fe(4)(OH)(4)(C(6)H(4)O(7))(4)](8-) (U(2)Fe(4))) that were characterized by single-crystal X-ray diffraction and vibrational spectroscopy. Mass spectroscopy was then employed to compare the model compounds to species present in aqueous solutions to provide an enhanced understanding of the ternary uranyl citrate complexes that could be relevant in natural systems.

Dehydration of the Uranyl Peroxide Studtite, [UO 2(η 2-O 2)(H 2O) 2]·2H 2O, Affords a Drastic Change in the Electronic Structure: A Combined X-ray Spectroscopic and Theoretical Analysis

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

Vitova, Tonya; Pidchenko, Ivan; Biswas, Saptarshi

The dehydration of studtite, [UO 2(2-O 2)(H 2O)2]·2H 2O, to metastudtite, [UO 2(2-O 2)(H 2O) 2], uranyl peroxide minerals that are major oxidative alteration phases of UO2 under conditions of geological storage, has been studied using X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy. XPS of the U 4f region shows small but significant differences between studtite and metastudtite, with the 4f binding energy of studtite the highest reported for a uranyl mineral studied by this technique. Further information on the changes in the electronic structure was elucidated using U M4-edge High Energy Resolution XANES (HR-XANES) spectroscopy, which directly probesmore » f-orbital states. The transition from the 3d to the 5f* orbital is sensitive to variations of the U=Oaxial bond length and to changes in the bond covalency. We report evidences that the covalence in the uranyl fragment decreases upon dehydration. Photoluminescence spectroscopy at near liquid helium temperatures reveals significant spectral differences between the two materials, correlating with the X-ray spectroscopy results. A theoretical investigation has been conducted on the structures of both studtite and metastudtite and benchmarked to the HR-XANES spectra. These illustrate the sensitivity of the 3d to the 5f * transition towards U=Oaxial bond variation.« less

Impact of pore size on the sorption of uranyl under seawater conditions

DOE PAGES

Mayes, Richard T.; Gorka, Joanna; Dai, Sheng

2016-04-05

The extraction of uranium from seawater has received significant interest recently, because of the possibility of a near-limitless supply of uranium to fuel the nuclear power industry. While sorbent development has focused primarily on polymeric sorbents, nanomaterials represent a new area that has the potential to surpass the current polymeric sorbents, because of the high surface areas that are possible. Mesoporous carbon materials are a stable, high-surface-area material capable of extracting various chemical species from a variety of environments. Herein, we report the use of a dual templating process to understand the effect of pore size on the adsorption ofmore » uranyl ions from a uranyl brine consisting of seawater-relevant sodium, chloride, and bicarbonate ions. It was found that pore size played a more significant role in the effective use of the grafted polymer, leading to higher uranium capacities than the surface area. Furthermore, the pore size must be tailored to meet the demands of the extraction medium and analyte metal to achieve efficacy as an adsorbent.« less

Polymorphism in Alkali Metal Uranyl Nitrates: Synthesis and Crystal Structure of γ-K(UO2)(NO3)3

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

Jouffret, Laurent J.; Krivovichev, Sergey V.; Burns, Peter C.

2011-07-20

Single crystals of γ-K(UO2)(NO3)3 were prepared from aqueous solutions by evaporation. The crystal structure [orthorhombic, Pbca (61), a = 9.2559(3) Å, b = 12.1753(3) Å, c = 15.8076(5) Å, V = 1781.41(9) Å3, Z = 8] was determined by direct methods and refined to R1 = 0.0267 on the basis of 3657 unique observed reflections. The structure is composed of isolated anionic uranyl trinitrate units, [(UO2)(NO3)3]–, that are linked through eleven-coordinated K+ cations. Both known polymorphs of K(UO2)(NO3)3 (α- and γ-phases) can be considered as based upon sheets of isolated complex [(UO2)(NO3)3]– ions separated by K+ cations. The existence ofmore » polymorphism in the two K[UO2(NO3)3] polymorphs is due to the different packing modes of uranyl trinitrate clusters that adopt the same two-dimensional but different three-dimensional arrangements.« less

Probing the oxygen environment in UO(2)(2+) by solid-state 17O nuclear magnetic resonance spectroscopy and relativistic density functional calculations.

PubMed

Cho, Herman; de Jong, Wibe A; Soderquist, Chuck Z

2010-02-28

A combined theoretical and solid-state (17)O nuclear magnetic resonance (NMR) study of the electronic structure of the uranyl ion UO(2)(2+) in (NH(4))(4)UO(2)(CO(3))(3) and rutherfordine (UO(2)CO(3)) is presented, the former representing a system with a hydrogen-bonding environment around the uranyl oxygens and the latter exemplifying a uranyl environment without hydrogens. Relativistic density functional calculations reveal unique features of the U-O covalent bond, including the finding of (17)O chemical shift anisotropies that are among the largest for oxygen ever reported (>1200 ppm). Computational results for the oxygen electric field gradient tensor are found to be consistently larger in magnitude than experimental solid-state (17)O NMR measurements in a 7.05 T magnetic field indicate. A modified version of the Solomon theory of the two-spin echo amplitude for a spin-5/2 nucleus is developed and applied to the analysis of the (17)O echo signal of U (17)O(2)(2+).

SEPARATION OF URANYL NITRATE BY EXTRACTION

DOEpatents

Stoughton, R.W.; Steahly, F.L.

1958-08-26

A process is presented for obtaining U/sup 233/ from solutions containing Pa/sup 233/. A carrier precipitate, such as MnO/sub 2/, is formed in such solutions and carries with it the Pa/sup 233/ present. This precipitate is then dissolved in nitric acid and the solution is aged to allow decay of the Pa/ sup 233/ into U/sup 233/. After a sufficient length of time the U/sup 233/ bearing solution is made 2.5 to 4.5 Molar in manganese nitrate by addition thereof, and the solution is then treated with ether to obtain uranyl nitrate by solvent extraction techniques.

ADSORPTION METHOD FOR SEPARATING THORIUM VALUES FROM URANIUM VALUES

DOEpatents

Boyd, G.E.; Russell, E.R.; Schubert, J.

1959-08-01

An improved ion exchange method is described for recovery of uranium and thorium values as separate functions from an aqueous acidic solution containing less than 10/sup -3/ M thorium ions and between 0.1 and 1 M uranyl ions. The solution is passed through a bed of cation exchange resin in the acid form to adsorb all the thorium ions and a portion of the uranyl ions. The uranium is eluted by means of aqueous 0.1 to 0.4 M sulfuric acid. The thorium may then be stripped from the resin by elution with aqueous 0.5 M oxalic acid.

ADSORPTION METHOD FOR SEPARATING THORIUM VALUES FROM URANIUM VALUES

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

Boyd, G.E.; Russell, E.R.; Schubert, J.

An improved ion exchange method is described for recovery of uranium and thorium values as separate functions from an aqueous acidic solution containing less than 10/sup -3/ M thorium ions and between 0.1 and 1 M uranyl ions. The solution is passed through a bed of cation exchange resin in the acid form to adsorb all the thorium ions and a portion of the uranyl ions. The uranium is eluted by means of aqueous 0.1 to 0.4 M sulfuric acid. The thorium may then be stripped from the resin by elution with aqueous 0.5 M oxalic acid.

A randomised clinical evaluation of a fluoride mouthrinse and dentifrice in an in situ caries model.

PubMed

Parkinson, Charles R; Hara, Anderson T; Nehme, Marc; Lippert, Frank; Zero, Domenick T

2018-03-01

Fluoride mouthrinses provide advantages for fluoride delivery by maintaining elevated intra-oral fluoride concentrations following fluoride dentifrice use. This in situ caries study investigated potential anti-caries efficacy of a 220 ppm fluoride mouthrinse. This was an analyst-blinded, four-treatment, randomised, crossover study using partially demineralised, gauze-wrapped, human enamel samples mounted in a mandibular partial denture. Participants brushed twice daily for 14 days with either a 1150 ppm fluoride or a fluoride-free placebo dentifrice and either rinsed once daily with the 220 ppm fluoride mouthrinse or not. Following each treatment period, percent surface microhardness recovery (%SMHR) and enamel fluoride uptake (EFU) were assessed. Fifty three participants completed the study. Compared with the placebo dentifrice/no rinse treatment, the fluoride-containing regimens demonstrated greater enamel remineralisation (%SMHR) and fluoridation (EFU): fluoride dentifrice/fluoride rinse (%SMHR difference: 21.55 [95% CI: 15.78,27.32]; EFU difference 8.35 [7.21,9.29]); fluoride dentifrice/no rinse: 19.48 [13.81,25.15]; 6.47 [5.35,7.60]; placebo dentifrice/fluoride rinse: 16.76 [11.06,22.45]; 5.87 [4.72,7.00] (all P < .0001). There were no significant differences in%SMHR between fluoride regimens. The fluoride dentifrice/fluoride rinse regimen was associated with higher EFU than the fluoride dentifrice/no rinse (1.88 [0.75,3.01], P = .0013) and placebo dentifrice/fluoride rinse regimens (2.48 [1.34,3.62], P < .0001). Treatments were generally well-tolerated. The in situ caries model demonstrated that the fluoride mouthrinse is effective in promoting enamel caries lesion remineralisation and fluoridation whether used following a fluoride or non-fluoride dentifrice. Additive (potential) anti-caries benefits of a fluoride rinse after a fluoride dentifrice were confined to enhancements in lesion fluoridation (EFU). In conjunction with a fluoride dentifrice, fluoride mouthrinses enhance enamel fluoridation, which may be useful in caries prevention. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

Contemporary biological markers of exposure to fluoride.

PubMed

Rugg-Gunn, Andrew John; Villa, Alberto Enrique; Buzalaf, Marília Rabelo Afonso

2011-01-01

Contemporary biological markers assess present, or very recent, exposure to fluoride: fluoride concentrations in blood, bone surface, saliva, milk, sweat and urine have been considered. A number of studies relating fluoride concentration in plasma to fluoride dose have been published, but at present there are insufficient data on plasma fluoride concentrations across various age groups to determine the 'usual' concentrations. Although bone contains 99% of the body burden of fluoride, attention has focused on the bone surface as a potential marker of contemporary fluoride exposure. From rather limited data, the ratio surface-to-interior concentration of fluoride may be preferred to whole bone fluoride concentration. Fluoride concentrations in the parotid and submandibular/sublingual ductal saliva follow the plasma fluoride concentration, although at a lower concentration. At present, there are insufficient data to establish a normal range of fluoride concentrations in ductal saliva as a basis for recommending saliva as a marker of fluoride exposure. Sweat and human milk are unsuitable as markers of fluoride exposure. A proportion of ingested fluoride is excreted in urine. Plots of daily urinary fluoride excretion against total daily fluoride intake suggest that daily urinary fluoride excretion is suitable for predicting fluoride intake for groups of people, but not for individuals. While fluoride concentrations in plasma, saliva and urine have some ability to predict fluoride exposure, present data are insufficient to recommend utilizing fluoride concentrations in these body fluids as biomarkers of contemporary fluoride exposure for individuals. Daily fluoride excretion in urine can be considered a useful biomarker of contemporary fluoride exposure for groups of people, and normal values have been published. Copyright © 2011 S. Karger AG, Basel.

Consistent Pl Analysis of Aqueous Uranium-235 Critical Assemblies

NASA Technical Reports Server (NTRS)

Fieno, Daniel

1961-01-01

The lethargy-dependent equations of the consistent Pl approximation to the Boltzmann transport equation for slowing down neutrons have been used as the basis of an IBM 704 computer program. Some of the effects included are (1) linearly anisotropic center of mass elastic scattering, (2) heavy element inelastic scattering based on the evaporation model of the nucleus, and (3) optional variation of the buckling with lethargy. The microscopic cross-section data developed for this program covered 473 lethargy points from lethargy u = 0 (10 Mev) to u = 19.8 (0.025 ev). The value of the fission neutron age in water calculated here is 26.5 square centimeters; this value is to be compared with the recent experimental value given as 27.86 square centimeters. The Fourier transform of the slowing-down kernel for water to indium resonance energy calculated here compared well with the Fourier transform of the kernel for water as measured by Hill, Roberts, and Fitch. This method of calculation has been applied to uranyl fluoride - water solution critical assemblies. Theoretical results established for both unreflected and fully reflected critical assemblies have been compared with available experimental data. The theoretical buckling curve derived as a function of the hydrogen to uranium-235 atom concentration for an energy-independent extrapolation distance was successful in predicting the critical heights of various unreflected cylindrical assemblies. The critical dimensions of fully water-reflected cylindrical assemblies were reasonably well predicted using the theoretical buckling curve and reflector savings for equivalent spherical assemblies.

Fluoride mechanisms.

PubMed

ten Cate, J M; van Loveren, C

1999-10-01

This article discusses fluoride mechanisms in relation to dental caries. The authors specifically address firmly bound versus loosely bound fluoride; different fluoride active ingredients; fluoride and demineralization and remineralization; fluoride slow-release devices and F-releasing dental materials; antimicrobial effects of fluoride; the uptake of fluoride by oral bacteria; inhibition of enolase, protein-intruding ATPase and sugar transport; the various aspects of plaque as it relates to fluoride; and the rational use of fluoride.

Computer simulation of uranyl uptake by the rough lipopolysaccharide membrane of Pseudomonas aeruginosa.

PubMed

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.

Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes.

PubMed

Perez, Evan; Hanley, Cassandra; Koehler, Stephen; Pestok, Jordan; Polonsky, Nevo; Van Stipdonk, Michael

2016-12-01

The speciation and reactivity of uranium are topics of sustained interest because of their importance to the development of nuclear fuel processing methods, and a more complete understanding of the factors that govern the mobility and fate of the element in the environment. Tandem mass spectrometry can be used to examine the intrinsic reactivity (i.e., free from influence of solvent and other condensed phase effects) of a wide range of metal ion complexes in a species-specific fashion. Here, electrospray ionization, collision-induced dissociation, and gas-phase ion-molecule reactions were used to create and characterize ions derived from precursors composed of uranyl cation (U VI O 2 2+ ) coordinated by formate or acetate ligands. Anionic complexes containing U VI O 2 2+ and formate ligands fragment by decarboxylation and elimination of CH 2 =O, ultimately to produce an oxo-hydride species [U VI O 2 (O)(H)] - . Cationic species ultimately dissociate to make [U VI O 2 (OH)] + . Anionic complexes containing acetate ligands exhibit an initial loss of acetyloxyl radical, CH 3 CO 2 •, with associated reduction of uranyl to U V O 2 + . Subsequent CID steps cause elimination of CO 2 and CH 4 , ultimately to produce [U V O 2 (O)] - . Loss of CH 4 occurs by an intra-complex H + transfer process that leaves U V O 2 + coordinated by acetate and acetate enolate ligands. A subsequent dissociation step causes elimination of CH 2 =C=O to leave [U V O 2 (O)] - . Elimination of CH 4 is also observed as a result of hydrolysis caused by ion-molecule reaction with H 2 O. The reactions of other anionic species with gas-phase H 2 O create hydroxyl products, presumably through the elimination of H 2 . Graphical Abstract ᅟ.

Uranyl extraction by N,N-dialkylamide ligands studied using static and dynamic DFT simulations.

PubMed

Sieffert, Nicolas; Wipff, Georges

2015-02-14

We report DFT static and dynamic studies on uranyl complexes [UO(2)(NO(3))x(H(2)O)(y)L(z)](2-x) involved in the uranyl extraction from water to an "oil" phase (hexane) by an amide ligand L (N,N-dimethylacetamide). Static DFT results "in solution" (continuum SMD models for water and hexane) predict that the stepwise formation of [UO(2)(NO(3))(2)L(2)] from the UO(2)(H(2)O)(5)(2+) species is energetically favourable, and allow us to compare cis/trans isomers of penta- and hexa-coordinated complexes and key intermediates in the two solvents. DFT-MD simulations of [UO(2)(NO(3))(2)L(2)], [UO(2)(NO(3))(2)(H(2)O)L(2)], and [UO(2)(NO(3))(H(2)O)L(2)](+) species in explicit solvent environments (water, hexane, or the water/hexane interface) represented at the MM or full-DFT level reveal a versatile solvent dependent binding mode of nitrates, also evidenced by metadynamics simulations. In water and at the interface, the latter exchange from bi- to monodentate, via in plane rotational motions in some cases. Remarkably, structures of complexes at the interface are more "water-like" than gas phase- or hexane-like. Thus, the order of U-O(NO(3))/U-O(L) bond distances observed in the gas phase (U-O(nit) < U-OL) is inverted at the interface and in water. Overall, the results are consistent with the experimental observation of uranyl extraction from nitric acid solutions by amide analogues (bearing "fatty" substituents), and allow us to propose possible extraction mechanisms, involving complexation of L "right at the interface". They also point to the importance of the solvent environment and the dynamics on the structure and stability of the complexes.

Dehydration of Uranyl Nitrate Hexahydrate to Uranyl Nitrate Trihydrate under Ambient Conditions as Observed via Dynamic Infrared Reflectance Spectroscopy

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

Johnson, Timothy J.; Sweet, Lucas E.; Meier, David E.

2015-05-22

the hexahydrate [UO 2(NO 3) 2(H 2O) 6] (UNH) and the trihydrate [UO 2(NO 3) 2(H 2O) 3] (UNT) forms. Their stabilities depend on both relative humidity and temperature. Both phases have previously been studied by infrared transmission spectroscopy, but the data were limited by both instrumental resolution and the ability to prepare the samples as pellets without desiccating them. We report time-resolved infrared (IR) measurements using an integrating sphere that allow us to observe the transformation from the hexahydrate to the trihydrate simply by flowing dry nitrogen gas over the sample. Hexahydrate samples were prepared and confirmed via knownmore » XRD patterns, then measured in reflectance mode. The hexahydrate has a distinct uranyl asymmetric stretch band at 949.0 cm -1 that shifts to shorter wavelengths and broadens as the sample dehydrates and recrystallizes to the trihydrate, first as a blue edge shoulder but ultimately resulting in a doublet band with reflectance peaks at 966 and 957 cm -1. The data are consistent with transformation from UNH to UNT since UNT has two non-equivalent UO 2 2+ sites. The dehydration of UO 2(NO 3) 2(H 2O) 6 to UO 2(NO 3) 2(H 2O) 3 is both a morphological and structural change that has the lustrous lime green crystals changing to the dull greenish yellow of the trihydrate. Crystal structures and phase transformation were confirmed theoretically using DFT calculations and experimentally via microscopy methods. Both methods showed a transformation with two distinct sites for the uranyl cation in the trihydrate, as opposed to a single crystallographic site in the hexahydrate.« less

Synthesis and X-ray diffraction study of new uranyl malonate and oxalate complexes with carbamide

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

Medvedkov, Ya. A.; Serezhkina, L. B., E-mail: Lserezh@samsu.ru; Grigor’ev, M. S.

2016-05-15

Two new malonate-containing uranyl complexes with carbamide of the formulas [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Urea){sub 2}] (I) and [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Urea){sub 3}] (II), where Urea is carbamide, and one uranyl oxalate complex of the formula [UO{sub 2}(C{sub 2}O{sub 4})(Urea){sub 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{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Urea){sub 2}]{sub ∞} belonging to the crystal-chemical group AT{sup 11}M{sub 2}{sup 1} (A = UO{sub 2}{sup 2+}, T{sup 11} = C{sub 3}H{sub 2}O{sub 4}{sup 2-}, M{sup 1} = Urea) of uranyl complexes.more » Crystals II and III are composed of the molecular complexes [UO{sub 2}(L)(Urea){sub 3}], where L = C{sub 3}H{sub 2}O{sub 4}{sup 2-} or C{sub 2}O{sub 4}{sup 2-}, belonging to the crystal-chemical group AB{sup 01}M{sub 3}{sup 1} (A = UO{sub 2}{sup 2+}, B{sup 01} = C{sub 3}H{sub 2}O{sub 4}{sup 2-} or C{sub 2}O{sub 4}{sup 2-}, M{sup 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.« less

Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes

NASA Astrophysics Data System (ADS)

Perez, Evan; Hanley, Cassandra; Koehler, Stephen; Pestok, Jordan; Polonsky, Nevo; Van Stipdonk, Michael

2016-12-01

The speciation and reactivity of uranium are topics of sustained interest because of their importance to the development of nuclear fuel processing methods, and a more complete understanding of the factors that govern the mobility and fate of the element in the environment. Tandem mass spectrometry can be used to examine the intrinsic reactivity (i.e., free from influence of solvent and other condensed phase effects) of a wide range of metal ion complexes in a species-specific fashion. Here, electrospray ionization, collision-induced dissociation, and gas-phase ion-molecule reactions were used to create and characterize ions derived from precursors composed of uranyl cation (UVIO2 2+) coordinated by formate or acetate ligands. Anionic complexes containing UVIO2 2+ and formate ligands fragment by decarboxylation and elimination of CH2=O, ultimately to produce an oxo-hydride species [UVIO2(O)(H)]-. Cationic species ultimately dissociate to make [UVIO2(OH)]+. Anionic complexes containing acetate ligands exhibit an initial loss of acetyloxyl radical, CH3CO2•, with associated reduction of uranyl to UVO2 +. Subsequent CID steps cause elimination of CO2 and CH4, ultimately to produce [UVO2(O)]-. Loss of CH4 occurs by an intra-complex H+ transfer process that leaves UVO2 + coordinated by acetate and acetate enolate ligands. A subsequent dissociation step causes elimination of CH2=C=O to leave [UVO2(O)]-. Elimination of CH4 is also observed as a result of hydrolysis caused by ion-molecule reaction with H2O. The reactions of other anionic species with gas-phase H2O create hydroxyl products, presumably through the elimination of H2.

UO₂²⁺ uptake by proteins: understanding the binding features of the super uranyl binding protein and design of a protein with higher affinity.

PubMed

Odoh, Samuel O; Bondarevsky, Gary D; Karpus, Jason; Cui, Qiang; He, Chuan; Spezia, Riccardo; Gagliardi, Laura

2014-12-17

The capture of uranyl, UO2(2+), by a recently engineered protein (Zhou et al. Nat. Chem. 2014, 6, 236) with high selectivity and femtomolar sensitivity has been examined by a combination of density functional theory, molecular dynamics, and free-energy simulations. It was found that UO2(2+) is coordinated to five carboxylate oxygen atoms from four amino acid residues of the super uranyl binding protein (SUP). A network of hydrogen bonds between the amino acid residues coordinated to UO2(2+) and residues in its second coordination sphere also affects the protein's uranyl binding affinity. Free-energy simulations show how UO2(2+) capture is governed by the nature of the amino acid residues in the binding site, the integrity and strength of the second-sphere hydrogen bond network, and the number of water molecules in the first coordination sphere. Alteration of any of these three factors through mutations generally results in a reduction of the binding free energy of UO2(2+) to the aqueous protein as well as of the difference between the binding free energies of UO2(2+) and other ions (Ca(2+), Cu(2+), Mg(2+), and Zn(2+)), a proxy for the protein's selectivity over these ions. The results of our free-energy simulations confirmed the previously reported experimental results and allowed us to discover a mutant of SUP, specifically the GLU64ASP mutant, that not only binds UO2(2+) more strongly than SUP but that is also more selective for UO2(2+) over other ions. The predictions from the computations were confirmed experimentally.

Divalent fluoride doped cerium fluoride scintillator

DOEpatents

Anderson, David F.; Sparrow, Robert W.

1991-01-01

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

Fluoride intake of infants living in non-fluoridated and fluoridated areas.

PubMed

Zohoori, F V; Whaley, G; Moynihan, P J; Maguire, A

2014-01-01

Data on fluoride exposure of infants are sparse. This study aimed to estimate total daily fluoride intake (TDFI) of infants aged 1-12 months, living in non-fluoridated and fluoridated areas in north-east England. Daily dietary fluoride intake was assessed using a three-day food diary coupled with analysis of fluoride content of food/drink consumed, using a F-ISE and diffusion method. A questionnaire with an interview was used to collect information on toothbrushing habits. TDFI was estimated from diet, plus fluoride supplements and dentifrice ingestion where used. Thirty-eight infants completed the study; 19 receiving fluoridated water (mean 0.97 mgF/l) and 19 receiving non-fluoridated water (mean 0.19 mgF/l). Mean (SD) TDFI for the infants living in fluoridated and non-fluoridated areas was 0.107 (0.054) and 0.024 (0.015) mg/kg body weight per day, respectively. Diet was the only fluoride source for 87% of infants and none used fluoride supplements. For infants for whom mouth/teeth cleaning was undertaken, dentifrice contribution to TDFI ranged from 24 to 78%. Infants living in fluoridated areas, in general, may receive a fluoride intake, from diet only, of more than the suggested optimal range for TDFI. This emphasises the importance of estimating TDFI at an individual level when recommendations for fluoride use are being considered.

Estimated dietary fluoride intake for New Zealanders.

PubMed

Cressey, Peter; Gaw, Sally; Love, John

2010-01-01

Existing fluoride concentration and consumption data were used to estimate fluoride intakes from the diet and toothpaste use, for New Zealand subpopulations, to identify any population groups at risk of high-fluoride intake. For each sub-population, two separate dietary intake estimates were made--one based on a non-fluoridated water supply (fluoride concentration of 0.1 mg/L), and the other based on a water supply fluoridated to a concentration of 1.0 mg/L. Fluoride concentration data were taken from historical surveys, while food consumption data were taken from national 24-hour dietary recall surveys or from simulated diets. Mean and 95th percentile estimations of dietary fluoride intake were well below the upper level of intake (UL), whether intakes were calculated on the basis of a non-fluoridated or fluoridated water supply. The use of fluoride-containing toothpastes provides additional fluoride intake. For many of the population groups considered, mean fluoride intakes were below the adequate intake (AI) level for caries protection, even after inclusion of the fluoride contribution from toothpaste. Intake of fluoride was driven by consumption of dietary staples (bread, potatoes),beverages (particularly tea, soft drinks, and beer), and the fluoride status of drinking water. Estimates of fluoride intake from the diet and toothpaste did not identify any groups at risk of exceeding the UL, with the exception of infants (6-12 months) living in areas with fluoridated water supplies and using high-fluoride toothpaste. In contrast, much of the adult population may be receiving insufficient fluoride for optimum caries protection from these sources, as represented by the AI.

Protein Hydrogel Microbeads for Selective Uranium Mining from Seawater.

PubMed

Kou, Songzi; Yang, Zhongguang; Sun, Fei

2017-01-25

Practical methods for oceanic uranium extraction have yet to be developed in order to tap into the vast uranium reserve in the ocean as an alternative energy. Here we present a protein hydrogel system containing a network of recently engineered super uranyl binding proteins (SUPs) that is assembled through thiol-maleimide click chemistry under mild conditions. Monodisperse SUP hydrogel microbeads fabricated by a microfluidic device further enable uranyl (UO 2 2+ ) enrichment from natural seawater with great efficiency (enrichment index, K = 2.5 × 10 3 ) and selectivity. Our results demonstrate the feasibility of using protein hydrogels to extract uranium from the ocean.

Chemical controls on uranyl citrate speciation and the self-assembly of nanoscale macrocycles and sandwich complexes in aqueous solutions.

PubMed

Basile, M; Unruh, D K; Gojdas, K; Flores, E; Streicher, L; Forbes, T Z

2015-03-28

Uranyl citrate forms trimeric species at pH > 5.5, but exact structural characteristics of these important oligomers have not previously been reported. Crystallization and structural characterization of the trimers suggests the self-assembly of the 3 : 3 and 3 : 2 U : Cit complexes into larger sandwich and macrocyclic molecules. Raman spectroscopy and ESI-MS have been utilized to investigate the relative abundance of these species in solution under varying pH and citrate concentrations. Additional dynamic light scattering experiments indicate that self-assembly of the larger molecules does occur in aqueous solution.

2,6-Diiminopiperidin-1-ol: an overlooked motif relevant to uranyl and transition metal binding on poly(amidoxime) adsorbents

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

Kennedy, Zachary C.; Cardenas, Allan Jay P.; Corbey, Jordan F.

2016-01-01

Glutardiamidoxime, a structural motif on sorbents used in uranium extraction from seawater, was discovered to cyclize in situ at room temperature to 2,6-diimino-piperidin-1-ol in the presence of uranyl nitrate. The new diimino motif was also generated when exposed to competing transition metals Cu(II) and Ni(II). Multinuclear μ-O bridged U(VI), Cu(II), and Ni(II) complexes featuring bound diimino ligands were isolated. A Cu(II) complex with the historically relevant cyclic imide dioxime motif is also reported for structural comparison to the reported diimino complexes.

Observation of a brine layer on an ice surface with an environmental scanning electron microscope at higher pressures and temperatures.

PubMed

Krausko, Ján; Runštuk, Jiří; Neděla, Vilém; Klán, Petr; Heger, Dominik

2014-05-20

Observation of a uranyl-salt brine layer on an ice surface using backscattered electron detection and ice surface morphology using secondary-electron detection under equilibrium conditions was facilitated using an environmental scanning electron microscope (ESEM) at temperatures above 250 K and pressures of hundreds of Pa. The micrographs of a brine layer over ice grains prepared by either slow or shock freezing provided a complementary picture of the contaminated ice grain boundaries. Fluorescence spectroscopy of the uranyl ions in the brine layer confirmed that the species exists predominately in the solvated state under experimental conditions of ESEM.

A ω-mercaptoundecylphosphonic acid chemically modified gold electrode for uranium determination in waters in presence of organic matter.

PubMed

Merli, Daniele; Protti, Stefano; Labò, Matteo; Pesavento, Maria; Profumo, Antonella

2016-05-01

A chemically modified electrode (CME) on a gold surface assembled with a ω-phosphonic acid terminated thiol was investigated for its capability to complex uranyl ions. The electrode, characterized by electrochemical techniques, demonstrated to be effective for the determination of uranyl at sub-μgL(-1) level by differential pulse adsorptive stripping voltammetry (DPAdSV) in environmental waters, also in presence of humic matter and other potential chelating agents. The accuracy of the measurements was investigated employing as model probes ligands of different complexing capability (humic acids and EDTA). Copyright © 2016 Elsevier B.V. All rights reserved.

Simultaneous reduction of arsenic(V) and uranium(VI) by mackinawite: role of uranyl arsenate precipitate formation.

PubMed

Troyer, Lyndsay D; Tang, Yuanzhi; Borch, Thomas

2014-12-16

Uranium (U) and arsenic (As) often occur together naturally and, as a result, can be co-contaminants at sites of uranium mining and processing, yet few studies have examined the simultaneous redox dynamics of U and As. This study examines the influence of arsenate (As(V)) on the reduction of uranyl (U(VI)) by the redox-active mineral mackinawite (FeS). As(V) was added to systems containing 47 or 470 μM U(VI) at concentrations ranging from 0 to 640 μM. In the absence of As(V), U was completely removed from solution and fully reduced to nano-uraninite (nano-UO2). While the addition of As(V) did not reduce U uptake, at As(V) concentrations above 320 μM, the reduction of U(VI) was limited due to the formation of a trögerite-like uranyl arsenate precipitate. The presence of U also significantly inhibited As(V) reduction. While less U(VI) reduction to nano-UO2 may take place in systems with high As(V) concentrations, formation of trögerite-like mineral phases may be an acceptable reclamation end point due to their high stability under oxic conditions.

Spectroscopy and DFT studies of uranyl carbonate, rutherfordine, UO2CO3: a model for uranium transport, carbon dioxide sequestration, and seawater species

NASA Astrophysics Data System (ADS)

Kalashnyk, N.; Perry, D. L.; Massuyeau, F.; Faulques, E.

2017-12-01

Several optical microprobe experiments of the anhydrous uranium carbonate—rutherfordine—are presented in this work and compared to periodic density functional theory results. Rutherfordine is the simplest uranyl carbonate and constitutes an ideal model system for the study of the rich uranium carbonate family relevant for environmental sustainability. Micro-Raman, micro-reflectance, and micro-photoluminescence (PL) spectroscopy studies have been carried out in situ on native, micrometer-sized crystals. The sensitivity of these techniques is sufficient to analyze minute amounts of samples in natural environments without using x-ray analysis. In addition, very intense micro-PL and micro-reflectance spectra that were not reported before add new results on the ground and excited states of this mineral. The optical gap value determined experimentally is found at about 2.6-2.8 eV. Optimized geometry, band structure, and phonon spectra have been calculated. The main vibrational lines are identified and predicted by this theoretical study. This work is pertinent for optical spectroscopy, for identification of uranyl species in various environmental settings, and for nuclear forensic analysis.

Effects of a low-radiotoxicity uranium salt (uranyl acetate) on biochemical and hematological parameters of the catfish, Clarias gariepinus

NASA Astrophysics Data System (ADS)

Al-Ghanim, Khalid A.; Ahmad, Zubair; Al-Kahem Al-Balawi, Hmoud F.; Al-Misned, Fahad; Maboob, Shahid; Suliman, El-Amin M.

2016-01-01

Specimens of Clarias gariepinus were treated with lethal (70, 75, 80, 85, 90, and 95 mg/L) and sub-lethal concentrations (8, 12 and 16 mg/L) of uranyl acetate, a low-radiotoxicity uranium salt. The LC 50 value was registered as 81.45 mg/L. The protein and glycogen concentrations in liver and muscles were decreased in the fish exposed to sub-lethal concentrations. The red blood cell (RBC) and white blood cell (WBC) counts, haemoglobin (Hb) concentration and haematocrit (Hct) values were decreased. Different blood indices like mean corpuscular volume (MCV), mean corpuscular haemoglobin (MCH) and mean corpuscular haemoglobin concentration (MCHC) were negatively affected. Level of plasma glucose was elevated whereas protein was decreased. The level of calcium concentration (Ca) was declined in the blood of exposed fish whereas magnesium (Mg) remains unchanged. The activity level of glutamic-oxaloacetic transaminase (GOT) and glutamic-pyruvic transaminase (GPT) was elevated in exposed fish. These effects were more pronounced in the last period of exposure and in higher concentrations. Results of the present study indicate that uranyl acetate has adverse effects on Clarias gariepinus and causes changes in the biochemical and hematological parameters of the fish.

Site-specific incorporation of uranyl carbonate species at the calcite surface

NASA Astrophysics Data System (ADS)

Reeder, Richard J.; Elzinga, Evert J.; Tait, C. Drew; Rector, K. D.; Donohoe, Robert J.; Morris, David E.

2004-12-01

Spatially resolved luminescence spectra from U(VI) co-precipitated at the (101¯4) growth surface of synthetic calcite single crystals confirm heterogeneous incorporation corresponding to the distribution of structurally non-equivalent steps composing the vicinal surfaces of spiral growth hillocks. Spectral structure from U(VI) luminescence at the "-" vicinal regions and featureless, weak luminescence at the "+" vicinal regions are consistent with previously reported observations of enrichment at the former sites during calcite growth. Luminescence spectra differ between the non-equivalent regions of the crystal, with the spectral features from the "-" vicinal region corresponding to those observed in bulk calcite samples. Subtle spectral shifts are observed from U(VI) co-precipitated with microcrystalline calcite synthesized by a different method, and all of the U(VI)-calcite sample spectra differ significantly from that of U(VI) co-precipitated with aragonite. The step-selective incorporation of U(VI) can be explained by a proposed model in which the allowed orientation for adsorption of the dominant calcium uranyl triscarbonate species is controlled by the atomic arrangement at step edges. Differences in the tilt angles of carbonate groups between non-equivalent growth steps favor adsorption of the calcium uranyl triscarbonate species at "-" steps, as observed in experiments.

Nuclear forensics investigation of morphological signatures in the thermal decomposition of uranyl peroxide.

PubMed

Schwerdt, Ian J; Olsen, Adam; Lusk, Robert; Heffernan, Sean; Klosterman, Michael; Collins, Bryce; Martinson, Sean; Kirkham, Trenton; McDonald, Luther W

2018-01-01

The analytical techniques typically utilized in a nuclear forensic investigation often provide limited information regarding the process history and production conditions of interdicted nuclear material. In this study, scanning electron microscopy (SEM) analysis of the surface morphology of amorphous-UO 3 samples calcined at 250, 300, 350, 400, and 450°C from uranyl peroxide was performed to determine if the morphology was indicative of the synthesis route and thermal history for the samples. Thermogravimetic analysis-mass spectrometry (TGA-MS) and differential scanning calorimetry (DSC) were used to correlate transitions in the calcined material to morphological transformations. The high-resolution SEM images were processed using the Morphological Analysis for Material Attribution (MAMA) software. Morphological attributes, particle area and circularity, indicated significant trends as a result of calcination temperature. The quantitative morphological analysis was able to track the process of particle fragmentation and subsequent sintering as calcination temperature was increased. At the 90% confidence interval, with 1000 segmented particles, the use of Kolmogorov-Smirnov statistical comparisons allowed discernment between all calcination temperatures for the uranyl peroxide route. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Oxo-exchange of gas-phase uranyl, neptunyl, and plutonyl with water and methanol.

PubMed

Lucena, Ana F; Odoh, Samuel O; Zhao, Jing; Marçalo, Joaquim; Schreckenbach, Georg; Gibson, John K

2014-02-17

A challenge in actinide chemistry is activation of the strong bonds in the actinyl ions, AnO2(+) and AnO2(2+), where An = U, Np, or Pu. Actinyl activation in oxo-exchange with water in solution is well established, but the exchange mechanisms are unknown. Gas-phase actinyl oxo-exchange is a means to probe these processes in detail for simple systems, which are amenable to computational modeling. Gas-phase exchange reactions of UO2(+), NpO2(+), PuO2(+), and UO2(2+) with water and methanol were studied by experiment and density functional theory (DFT); reported for the first time are experimental results for UO2(2+) and for methanol exchange, as well as exchange rate constants. Key findings are faster exchange of UO2(2+) versus UO2(+) and faster exchange with methanol versus water; faster exchange of UO2(+) versus PuO2(+) was quantified. Computed potential energy profiles (PEPs) are in accord with the observed kinetics, validating the utility of DFT to model these exchange processes. The seemingly enigmatic result of faster exchange for uranyl, which has the strongest oxo-bonds, may reflect reduced covalency in uranyl as compared with plutonyl.

New insight into the ternary complexes of uranyl carbonate in seawater.

PubMed

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.

Fluoride toothpastes and fluoride mouthrinses for home use.

PubMed

Rugg-Gunn, Andrew; Bánóczy, Jolán

2013-11-01

To provide a brief commentary review of fluoride-containing toothpastes and mouthrinses with emphasis on their use at home. Toothpastes and mouthrinses are just two of many ways of providing fluoride for the prevention of dental caries. The first investigations into incorporating fluoride into toothpastes and mouthrinses were reported in the middle 1940s. Unlike water fluoridation (which is 'automatic fluoridation'), fluoride-containing toothpastes and fluoridecontaining mouthrinses are, primarily, for home use and need to be purchased by the individual. By the 1960s, research indicated that fluoride could be successfully incorporated into toothpastes and clinical trials demonstrated their effectiveness. By the end of the 1970s, almost all toothpastes contained fluoride. The widespread use of fluoride- containing toothpastes is thought to be the main reason for much improved oral health in many countries. Of the many fluoride compounds investigated, sodium fluoride, with a compatible abrasive, is the most popular, although amine fluorides are used widely in Europe. The situation is similar for mouthrinses. Concentrations of fluoride (F), commonly found, are 1500 ppm (1500 μg F/g) for toothpastes and 225 ppm (225 μg F/ml) for mouthrinse. Several systematic reviews have concluded that fluoride-containing toothpastes and mouthrinses are effective, and that there is added benefit from their use with other fluoride delivery methods such as water fluoridation. Guidelines for the appropriate use of fluoride toothpastes and mouthrinses are available in many countries. Fluoride toothpastes and mouthrinses have been developed and extensive testing has demonstrated that they are effective and their use should be encouraged. Copyright © 2013 by Academy of Sciences and Arts of Bosnia and Herzegovina.

Oral fluoride retention after use of fluoride dentifrices.

PubMed

Duckworth, R M; Morgan, S N

1991-01-01

Fluoride is the only extensively clinically proven means of reducing dental caries. Despite a large body of epidemiological data on the effectiveness of fluoride, delivered in the form of dentifrices, mouthrinses, drinking water, etc., the precise mode of action of fluoride is not completely understood. The purpose of this paper is to report an investigation of the link between oral fluoride levels and applied fluoride dose from dentifrices. Human salivary fluoride clearance studies and equilibrium baseline studies of fluoride in saliva and plaque have been carried out with dentifrices which contained 1,000, 1,500 and 2,500 micrograms fluoride per gram as sodium monofluorophosphate. After a single brushing with a fluoride dentifrice, salivary fluoride decreased in two distinct phases: an initial rapid phase which lasted for 40-80 min, depending on the individual, and a second slow phase lasting for several hours. The latter phase is believed to be due to fluoride released from an oral fluoride reservoir. During regular repeated use of the test dentifrices, the equilibrium baseline fluoride concentration, attained in both saliva and plaque between one application and the next, increased significantly compared with placebo values. Such elevated baseline fluoride concentrations also increased with increasing Na2FPO3 content of the dentifrices. The present work supports the concept that labile fluoride, stored in an oral fluoride reservoir at the time of treatment application, may maintain a prolonged protective effect against dental caries.

Calibration of equipment for analysis of drinking water fluoride: a comparison study.

PubMed

Quock, Ryan L; Chan, Jarvis T

2012-03-01

Current American Dental Association evidence-based recommendations for prescription of dietary fluoride supplements are based in part on the fluoride concentration of a pediatric patient's drinking water. With these recommendations in mind, this study compared the relative accuracy of fluoride concentration analysis when a common apparatus is calibrated with different combinations of standard values. Fluoride solutions in increments of 0.1 ppm, from a range of 0.1 to 1.0 ppm fluoride, as well as 2.0 and 4.0 ppm, were gravimetrically prepared and fluoride concentration measured in pentad, using a fluoride ion-specific electrode and millivolt meter. Fluoride concentrations of these solutions were recorded after calibration with the following 3 different combinations of standard fluoride solutions: 0.1 ppm and 0.5 ppm, 0.1 ppm and 1.0 ppm, 0.5 ppm and 1.0 ppm. Statistical analysis showed significant differences in the fluoride content of water samples obtained with different two-standard fluoride solutions. Among the two-standard fluoride solutions tested, using 0.5 ppm and 1.0 ppm as two-standard fluoride solutions provided the most accurate fluoride measurement of water samples containing fluoride in the range of 0.1 ppm to 4.0 ppm. This information should be valuable to dental clinics or laboratories in fluoride analysis of drinking water samples.

Structural, spectroscopic and redox properties of uranyl complexes with a maleonitrile containing ligand.

PubMed

Hardwick, Helen C; Royal, Drew S; Helliwell, Madeleine; Pope, Simon J A; Ashton, Lorna; Goodacre, Roy; Sharrad, Clint A

2011-06-14

The reaction of uranyl nitrate hexahydrate with the maleonitrile containing Schiff base 2,3-bis[(4-diethylamino-2-hydroxybenzylidene)amino]but-2-enedinitrile (salmnt((Et(2)N)(2))H(2)) in methanol produces [UO(2)(salmnt((Et2N)2))(H(2)O)] (1) where the uranyl equatorial coordination plane is completed by the N(2)O(2) tetradentate cavity of the (salmnt((Et(2)N)(2)))(2-) ligand and a water molecule. The coordinated water molecule readily undergoes exchange with pyridine (py), dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF) and triphenylphosphine oxide (TPPO) to give a series of [UO(2)(salmnt((Et(2)N)(2)))(L)] complexes (L = py, DMSO, DMF, TPPO; 2-5, respectively). X-Ray crystallography of 1-5 show that the (salmnt((Et(2)N)(2)))(2-) ligand is distorted when coordinated to the uranyl moiety, in contrast to the planar structure observed for the free protonated ligand (salmnt((Et(2)N)(2))H(2)). The Raman spectra of 1-5 only display extremely weak bands (819-828 cm(-1)) that can be assigned to the typically symmetric O=U=O stretch. This stretching mode is also observed in the infrared spectra for all complexes 1-5 (818-826 cm(-1)) predominantly caused by the distortion of the tetradentate (salmnt((Et(2)N)(2)))(2-) ligand about the uranyl equatorial plane resulting in a change in dipole for this bond stretch. The solution behaviour of 2-5 was studied using NMR, electronic absorption and emission spectroscopy, and cyclic voltammetry. Complexes 2-5 exhibit intense absorptions in the visible region of the spectrum due to intramolecular charge transfer (ICT) transitions and the luminescence lifetimes (< 5 ns) indicate the emission arises from ligand-centred excited states. Reversible redox processes assigned to the {UO(2)}(2+)/{UO(2)}(+) couple are observed for complexes 2-5 (2: E(1/2) = -1.80 V; 3,5: E(1/2) = -1.78 V; 4: E(1/2) = -1.81 V : vs. ferrocenium/ferrocene {Fc(+)/Fc}, 0.1 M Bu(4)NPF(6)) in dichloromethane (DCM). These are some of the most negative half potentials for the {UO(2)}(2+)/{UO(2)}(+) couple observed to date and indicate the strong electron donating nature of the (salmnt((Et(2)N)(2)))(2-) ligand. Multiple uranyl redox processes are clearly seen for [UO(2)(salmnt((Et(2)N)(2)))(L)] in L (L = py, DMSO, DMF; 2-4: 0.1 M Bu(4)NPF(6)) indicating the relative instability of these complexes when competing ligands are present, but the reversible {UO(2)}(2+)/{UO(2)}(+) couple for the intact complexes can still be assigned and shows the position of this couple can be modulated by the solvation environment. Several redox processes were also observed between +0.2 and +1.2 V (vs. Fc(+)/Fc) that prove the redox active nature of the maleonitrile-containing ligand.

Cation–cation interactions and cation exchange in a series of isostructural framework uranyl tungstates

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

Balboni, Enrica; Burns, Peter C., E-mail: pburns@nd.edu; Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556

2014-05-01

The isotypical compounds (UO{sub 2}){sub 3}(WO{sub 6})(H{sub 2}O){sub 5} (1), Ag(UO{sub 2}){sub 3}(WO{sub 6})(OH)(H{sub 2}O){sub 3} (2), K(UO{sub 2}){sub 3}(WO{sub 6})OH(H{sub 2}O){sub 4} (3), Rb(UO{sub 2}){sub 3}(WO{sub 6})(OH)(H{sub 2}O){sub 3.5} (4), and Cs(UO{sub 2}){sub 3}(WO{sub 6})OH(H{sub 2}O){sub 3} (5) were synthesized, characterized, and their structures determined. Each crystallizes in space group Cc. (1): a=12.979 (3), b=10.238 (2), c=11.302 (2), β=102.044 (2); (2): a=13.148 (2), b=9.520 (1), c=11.083 (2), β=101.568 (2); (3): a=13.111 (8), b=9.930 (6), c=11.242 (7), β=101.024 (7); (4): a=12.940 (2), b=10.231 (2), c=11.259(2), β=102.205 (2); (5): a=12.983 (3), b=10.191 (3), c=11.263 (4), β=101.661 (4). Compounds 1–5 are amore » framework of uranyl and tungsten polyhedra containing cation–cation interactions. The framework has three symmetrically distinct U(VI) cations, one tungsten, sixteen to eighteen oxygen atoms, and in 2–5, one monovalent cation. Each atom occupies a general position. Each U(VI) cation is present as a typical (UO{sub 2}){sup 2+} uranyl ion in an overall pentagonal bipyramidal coordination environment. Each pentagonal bipyramid shares two equatorial edges with two other pentagonal bipyramids, forming a trimer. Trimers are connected into chains by edge-sharing with WO{sub 6} octahedra. Chains are linked through cation–cation interactions between two symmetrically independent uranyl ions. This yields a remarkably complex system of intersecting channels that extend along [0 0 1] and [−1 1 0]. The cation exchange properties of 2 and 3 were characterized at room temperature and at 140 °C. - Graphical abstract: Chains of uranium and tungsten polyhedra are connected into a three dimensional framework by cation–cation interactions occurring between two symmetrically independent uranyl pentagonal bipyramids. Monovalent cations present in channels within the structure can be exchanged by room temperature or mild hydrothermal treatments. The framework of these compounds is robust to cation exchange and heat. (yellow polyhedra=uranium pentagonal bipyramids; blue polyhedra=tungsten octahedral, purple balls=K; yellow balls=Na; grey balls=Tl). - Highlights: • Five isostructural uranyl tungstates compounds were synthesized hydrothermally. • The structures consist of a chains of uranium and tungstate polyhedral. • Chains are connected into a framework by cation–cation interactions. • Cation exchange does not alter the structural integrity of the compounds. • Cation exchange was successful at room temperature and mild hydrothermal conditions.« less

Molecular Simulations of the Diffusion of Uranyl Carbonate Species in Nanosized Mineral Fractures

NASA Astrophysics Data System (ADS)

Kerisit, S.; Liu, C.

2010-12-01

Uranium is a major groundwater contaminant at uranium processing and mining sites as a result of intentional and accidental discharges of uranium-containing waste products into subsurface environments. Recent characterization has shown that uranium preferentially associates with intragrain and intra-aggregate domains in some of the uranium-contaminated sediments collected from the US Department of Energy Hanford Site [1, 2]. In these sediments, uranium existed as precipitated and/or adsorbed phases in grain micropores with nano- to microscale sizes. Desorption and diffusion characterization studies and continuum-scale modeling indicated that ion diffusion in the microfractures is a major mechanism that led to preferential uranium concentration in the microfracture regions and will control the future mobility of uranium in the subsurface sediments [1, 3-4]. However, the diffusion properties of uranyl species in the intragrain regions, especially at the solid-liquid interface, are still poorly understood. Therefore, a general aim of this work is to provide atomic-level insights into the contribution of microscopic surface effects to the slow diffusion process of uranyl species in porous media with nano- to microsized fractures. In this presentation, we will first present molecular dynamics (MD) simulations of feldspar-water interfaces to investigate their interfacial structure and dynamics and establish a theoretical framework for subsequent simulations of water and ion diffusion at these interfaces [5]. We will then report on MD simulations carried out to probe the effects of confinement and of the presence of the mineral surface on the diffusion of water and electrolyte ions in nanosized feldspar fractures [6]. Several properties of the mineral-water interface were varied, such as the fracture width, the ionic strength of the contacting solution, and the surface charge. Our calculations reveal a 2.0-2.5 nm interfacial region within which the diffusion properties of water and that of the electrolyte ions differ significantly from those in bulk aqueous solutions. We will then present MD simulations of the diffusion of a series of alkaline-earth uranyl carbonate species in aqueous solutions [7]. The MD simulations show that the alkaline-earth uranyl carbonate complexes have distinct water exchange dynamics, which could lead to different reactivities. Finally, we will present recent results on the diffusion and adsorption of uranyl carbonate species in intragrain micropores, modeled with the feldspar-water interfaces mentioned in the above, to help interpret the diffusion behavior of uranium in contaminated sediments. [1] Liu C. et al. Geochim. Cosmochim. Acta 68 4519 (2004) [2] McKinley J. P. et al. Geochim. Cosmochim. Acta 70 1873 (2006) [3] Liu C. et al. Water Resour. Res. 42 W12420 (2006) [4] Ilton E. S. et al. Environ. Sci. Technol. 42 1565 (2009) [5] Kerisit S. et al. Geochim. Cosmochim. Acta 72 1481 (2008) [6] Kerisit S. and Liu C. Environ. Sci. Technol. 43 777 (2009) [7] Kerisit S. and Liu C. Geochim. Cosmochim. Acta 74 4937 (2010)

Urinary fluoride excretion in preschool children after intake of fluoridated milk and use of fluoride-containing toothpaste.

PubMed

Norman, M; Twetman, S; Hultgren Talvilahti, A; Granström, E; Stecksén-Blicks, C

2017-03-01

To assess the urinary fluoride excretion in preschool children after drinking fluoridated milk with 0.185 mg F and 0.375 mg F and to study the impact of use of fluoride toothpaste. Double-blind cross-over study. Nine healthy children, 2.5-4.5 years of age. In a randomized order, participants drank 1.5 dl milk once daily for 7 days with no fluoride added (control), 0.185 mg fluoride added and 0.375 mg fluoride added. The experiment was performed twice with (Part I) and without (Part II) parental tooth brushing with 1,000 ppm fluoride toothpaste. The fluoride content in the piped drinking water was 0.5 mg F/L. Urinary fluoride excretion. The 24-hour urinary fl uoride excretion/kg body weight varied from 0.014 mg F for the placebo intervention and non-fluoride toothpaste to 0.027 mg F for the 0.375 mg intervention with use of 1,000 ppm fluoride toothpaste. The difference compared with the placebo intervention was not statistically significant for any of the interventions when fluoride toothpaste was used (p⟩0.05) while it was statistically significantly different when non-fluoride toothpaste was used (p⟨0.05). All sources of fluoride must be considered when designing community programs. With 0.5 mg F/L in the drinking water and daily use of fluoride toothpaste, most children had a fluoride intake optimal for dental health. In this setting, additional intake of fluoride milk was within safe limits up to 0.185 mg/day while conclusions about the safety of 0.375 mg/day were uncertain. Copyright© 2017 Dennis Barber Ltd

Determining the optimal fluoride concentration in drinking water for fluoride endemic regions in South India.

PubMed

Viswanathan, Gopalan; Jaswanth, A; Gopalakrishnan, S; Siva Ilango, S; Aditya, G

2009-10-01

Fluoride ion in drinking water is known for both beneficial and detrimental effects on health. The prevalence of fluorosis is mainly due to the intake of large quantities of fluoride through drinking water owing to more than 90% bioavailability. The objective of this study is to predict optimal fluoride level in drinking water for fluoride endemic regions by comprising the levels of fluoride and other water quality parameters in drinking water, prevalence of fluorosis, fluoride intake through water, food and beverages such as tea and coffee and also considering the progressive accumulation of fluoride in animal bones, by comparing with non fluoride endemic areas comprise of the same geological features with the aid of regression analysis. Result of this study shows that increase of fluoride level above 1.33 mg/l in drinking water increases the community fluorosis index (CFI) value more than 0.6, an optimum index value above which fluorosis is considered to be a public health problem. Regression plot between water fluoride and bone fluoride levels indicates that, every increase of 0.5mg/l unit of water fluoride level increases the bone fluoride level of 52 mg/kg unit within 2 to 3 years. Furthermore, the consumption of drinking water containing more than 0.65 mg/l of fluoride can raise the total fluoride intake per day more than 4 mg, which is the optimum fluoride dose level recommended for adults by the Agency for Toxic Substances and Disease Registry. From the result, the people in fluoride endemic areas in South India are advised to consume drinking water with fluoride level within the limit of 0.5 to 0.65 mg/l to avoid further fluorosis risk.

[The dose-effect relationship of water fluoride levels and renal damage in children].

PubMed

Liu, Jun-Ling; Xia, Tao; Yu, Yao-Yong; Sun, Xian-Zhong; Zhu, Qilong; He, Weihong; Zhang, Ming; Wang, Aiguo

2005-05-01

To explore the dose-effect relationship of water fluoride levels and renal damage in children and observe the difference of renal function between high-loaded fluoride people and dental fluorosis people in the same water fluoride level region. 210 children were divided into seven groups in term of drinking water fluoride levels and whether they suffered from dental fluorosis. Fluoride concentrations in urine and serum and activities of urine NAG and gamma-GT were determined. The urine and serum fluoride of high-loaded fluoride people and dental fluorosis people increased compared with control, moreover fluoride contents in urine and serum increased gradually with the increase of fluoride level in drinking water. Urine NAG and gamma-GT activities significantly increased in dental fluorosis people from area of 2.58 mg/L fluoride in drinking water and in those two groups from area of 4.51 mg/L fluoride in drinking water. Moreover, there existed an obvious dose-effect relationship between the drinking water fluoride concentration and NAG and gamma-GT activity. Over 2.0 mg/L fluoride in drinking water can cause renal damage in children, and the damage degree increases with the drinking water fluoride content. Renal damage degree is not related to whether the children suffered from dental fluorosis and mainly due to water fluoride concentration.

Urinary Fluoride Concentration in Children with Disabilities Following Long-Term Fluoride Tablet Ingestion

ERIC Educational Resources Information Center

Liu, Hsiu-Yueh; Chen, Jung-Ren; Hung, Hsin-Chia; Hsiao, Szu-Yu; Huang, Shun-Te; Chen, Hong-Sen

2011-01-01

Urine is the most commonly utilized biomarker for fluoride excretion in public health and epidemiological studies. Approximately 30-50% of fluoride is excreted from urine in children. Urinary fluoride excretion reflects the total fluoride intake from multiple sources. After administering fluoride tablets to children with disabilities, urinary…

Fluoride content of tank water in Australia.

PubMed

Cochrane, N J; Hopcraft, M S; Tong, A C; Thean, H l; Thum, Y S; Tong, D E; Wen, J; Zhao, S C; Stanton, D P; Yuan, Y; Shen, P; Reynolds, E C

2014-06-01

The aims of this study were to: (1) analyse the fluoride content of tank water; (2) determine whether the method of water collection or storage influenced fluoride content; and (3) survey participant attitudes towards water fluoridation. Plastic tubes and a questionnaire were distributed through dentists to households with water tanks in Victoria. A midstream tank water sample was collected and fluoride analysed in triplicate using ion chromatography All samples (n = 123) contained negligible amounts of fluoride, with a mean fluoride concentration of <0.01 ppm (range: <0.01-0.18 ppm). No statistically significant association was found between fluoride content and variables investigated such as tank material, tank age, roof material and gutter material. Most people did not know whether their tank water contained fluoride and 40.8% preferred to have access to fluoridated water. The majority thought fluoride was safe and more than half of the respondents supported fluoridation. Fluoride content of tank water was well below the optimal levels for caries prevention. People who rely solely on tank water for drinking may require additional exposure to fluoride for optimal caries prevention. © 2014 Australian Dental Association.

Kinetics of fluoride bioavailability in supernatant saliva and salivary sediment.

PubMed

Naumova, E A; Sandulescu, T; Bochnig, C; Gaengler, P; Zimmer, S; Arnold, W H

2012-07-01

The assessment of the fluoride kinetics in whole saliva as well as in the different salivary phases (supernatant saliva and sediment) is essential for the understanding of fluoride bioavailability. To assess the fluoride content, provided by sodium fluoride and amine fluoride, in the supernatant saliva and in salivary sediment. Seven trained volunteers were randomly attributed to 2 groups in a cross-over design and brushed their teeth in the morning for 3 min with a product containing either sodium fluoride or amine fluoride. Saliva was collected before, immediately after tooth brushing and 30, 120, and 360 min later and measured. The samples were centrifuged 10 min at 3024 × g. Fluoride content of the supernatant saliva and of the sediment was analysed using a fluoride sensitive electrode. All subjects repeated the study cycles 2 times, and statistical analyses were made using the nonparametric sign test for related samples, the Wilcoxon-Mann-Whitney-test for independent samples. There was a significant increase in fluoride immediately after tooth brushing in both groups in saliva and sediment. The distribution of fluoride between salivary sediment and supernatant saliva (ratio) varied considerably at the different collection times: decreased from 17.87 in baseline samples of saliva to 0.07 immediately and to 0.86 half an hour after tooth brushing in the sodium fluoride group and from 14.33 to 2.85 and to 3.09 in the amine fluoride group. Furthermore after 120 min and after 360 min after tooth brushing the ratio increased from 17.6 to 31.6 in the sodium fluoride group and from 20.5 to 25.76 in the amine fluoride group. No difference was found in the sediment-supernatant saliva ratio between the sodium fluoride and the amine fluoride groups 360 min after tooth brushing. For the assessment of fluoride kinetics in whole saliva it is necessary to pay attention to at least four factors: fluoride formulation, time after fluoride application, fluoride concentration in supernatant saliva and fluoride concentration in salivary sediment. This study was approved by the Ethical Committee of the University of Witten/Herdecke permission 21/2008. Copyright © 2012 Elsevier Ltd. All rights reserved.

Focus on Fluorides: Update on the Use of Fluoride for the Prevention of Dental Caries

PubMed Central

Carey, Clifton M.

2014-01-01

Declarative Title: Improving the efficacy of fluoride therapies reduces dental caries and lowers fluoride exposure. Background Fluoride is delivered to the teeth systemically or topically to aid in the prevention of dental caries. Systemic fluoride from ingested sources is in blood serum and can be deposited only in teeth that are forming in children. Topical fluoride is from sources such as community water, processed foods, beverages, toothpastes, mouthrinses, gels, foams, and varnishes. The United States Centers for Disease Control and Prevention (CDC) and the American Dental Association (ADA) have proposed changes in their long standing recommendations for the amount of fluoride in community drinking water in response to concerns about an increasing incidence of dental fluorosis in children. Current research is focused on the development of strategies to improve fluoride efficacy. The purpose of this update is to inform the reader about new research and policies related to the use of fluoride for the prevention of dental caries. Methods Reviews of the current research and recent evidence based systematic reviews on the topics of fluoride are presented. Topics discussed include: updates on community water fluoridation research and policies; available fluoride in dentifrices; fluoride varnish compositions, use, and recommendations; and other fluoride containing dental products. This update provides insights into current research and discusses proposed policy changes for the use of fluoride for the prevention of dental caries. Conclusions The dental profession is adjusting their recommendations for fluoride use based on current observations of the halo effect and subsequent outcomes. The research community is focused on improving the efficacy of fluoride therapies thus reducing dental caries and lowering the amount of fluoride required for efficacy. PMID:24929594

Focus on fluorides: update on the use of fluoride for the prevention of dental caries.

PubMed

Carey, Clifton M

2014-06-01

Improving the efficacy of fluoride therapies reduces dental caries and lowers fluoride exposure. Fluoride is delivered to the teeth systemically or topically to aid in the prevention of dental caries. Systemic fluoride from ingested sources is in blood serum and can be deposited only in teeth that are forming in children. Topical fluoride is from sources such as community water, processed foods, beverages, toothpastes, mouthrinses, gels, foams, and varnishes. The United States Centers for Disease Control and Prevention (CDC) and the American Dental Association (ADA) have proposed changes in their long standing recommendations for the amount of fluoride in community drinking water in response to concerns about an increasing incidence of dental fluorosis in children. Current research is focused on the development of strategies to improve fluoride efficacy. The purpose of this update is to inform the reader about new research and policies related to the use of fluoride for the prevention of dental caries. Reviews of the current research and recent evidence based systematic reviews on the topics of fluoride are presented. Topics discussed include: updates on community water fluoridation research and policies; available fluoride in dentifrices; fluoride varnish compositions, use, and recommendations; and other fluoride containing dental products. This update provides insights into current research and discusses proposed policy changes for the use of fluoride for the prevention of dental caries. The dental profession is adjusting their recommendations for fluoride use based on current observations of the halo effect and subsequent outcomes. The research community is focused on improving the efficacy of fluoride therapies thus reducing dental caries and lowering the amount of fluoride required for efficacy. Copyright © 2014 Elsevier Inc. All rights reserved.

The cariostatic mechanisms of fluoride.

PubMed

Rošin-Grget, Kata; Peroš, Kristina; Sutej, Ivana; Bašić, Krešimir

2013-11-01

This article discusses the possible cariostatic mechanisms of the action of fluoride. In the past, fluoride inhibition of caries was ascribed to reduced solubility of enamel due to incorporation of fluoride (F-) into the enamel minerals. The present evidence from clinical and laboratory studies suggests that the caries-preventive mode of action of fluoride is mainly topical. There is convincing evidence that fluoride has a major effect on demineralisation and remineralisation of dental hard tissue. The source of this fluoride could either be fluorapatite (formed due to the incorporation of fluoride into enamel) or calcium fluoride (CaF2)-like precipitates, which are formed on the enamel and in the plaque after application of topical fluoride. Calcium fluoride deposits are protected from rapid dissolution by a phosphate -protein coating of salivary origin. At lower pH, the coating is lost and an increased dissolution rate of calcium fluoride occurs. The CaF2, therefore, act as an efficient source of free fluoride ions during the cariogenic challenge. The current evidence indicates that fluoride has a direct and indirect effect on bacterial cells, although the in vivo implications of this are still not clear. A better understanding of the mechanisms of the action of fluoride is very important for caries prevention and control. The effectiveness of fluoride as a cariostatic agent depends on the availability of free fluoride in plaque during cariogenic challenge, i.e. during acid production. Thus, a constant supply of low levels of fluoride in biofilm/saliva/dental interference is considered the most beneficial in preventing dental caries. Copyright © 2013 by Academy of Sciences and Arts of Bosnia and Herzegovina.

Fluoride Supplementation Adherence and Barriers in a Community Without Water Fluoridation.

PubMed

Flood, Shannon; Asplund, Karin; Hoffman, Benjamin; Nye, Allison; Zuckerman, Katharine E

2017-04-01

To prevent early childhood caries, the American Dental Association recommends oral fluoride supplementation for children in communities lacking water fluoridation who are at high caries risk. However, patient adherence to oral fluoride supplementation has not been studied in this population. This study assessed adherence to oral fluoride and barriers to adherence in a community lacking water fluoridation. A self-administered survey was completed in a systematic sample of 209 parents of children aged 6 months to 4 years, during a primary care visit in an urban academic medical center. Participants reported frequency of administering oral fluoride to their children, as well as agreement or disagreement with proposed barriers to supplementation. Bivariate and multivariate analyses were used to assess adherence with oral supplementation and the association of barriers to supplementation and child receipt of fluoride on the day before. More than half of parents either had not or did not know if their child had received fluoride on the day before. Approximately 1 in 4 of parents had given fluoride in 0 of the previous 7 days. Difficulty remembering to give fluoride and agreeing that the child does not need extra fluoride were associated with not receiving fluoride on the day before. Adherence to oral fluoride supplementation in the primary care setting is low. Difficulty remembering to give fluoride daily is the greatest barrier to adherence. Further research on interventions to reduce common barriers is needed to increase fluoride administration and reduce early childhood caries in communities lacking water fluoridation. Copyright © 2016 Academic Pediatric Association. Published by Elsevier Inc. All rights reserved.

Oral fluoride levels 1 h after use of a sodium fluoride rinse: effect of sodium lauryl sulfate.

PubMed

Vogel, Gerald L; Schumacher, Gary E; Chow, Laurence C; Tenuta, Livia M A

2015-01-01

Increasing the concentration of free fluoride in oral fluids is an important goal in the use of topical fluoride agents. Although sodium lauryl sulfate (SLS) is a common dentifrice ingredient, the influence of this ion on plaque fluid and salivary fluid fluoride has not been examined. The purpose of this study was to investigate the effect of SLS on these parameters and to examine the effect of this ion on total (or whole) plaque fluoride, an important source of plaque fluid fluoride after a sufficient interval following fluoride administration, and on total salivary fluoride, a parameter often used as a surrogate measure of salivary fluid fluoride. Ten subjects accumulated plaque for 48 h before rinsing with a 12 mmol/l NaF (228 µg/g F) rinse containing or not containing 0.5% (w/w) SLS. SLS had no statistically significant effect on total plaque and total saliva fluoride but significantly increased salivary fluid and plaque fluid fluoride (by 147 and 205%, respectively). These results suggest that the nonfluoride components of topical agents can be manipulated to improve the fluoride release characteristics from oral fluoride reservoirs and that statistically significant change may be observed in plaque fluid and salivary fluid fluoride concentrations that may not be observed in total plaque and total saliva fluoride concentrations.

The effect of fluoridation and its discontinuation on fluoride profiles in the alveolar bone of rat.

PubMed

Ohmi, Kyohei; Nakagaki, Haruo; Tsuboi, Shinji; Okumura, Akihiro; Sugiyama, Tomoko; Thuy, Tran Thu; Robinson, Colin

2005-10-01

We investigated the effect of fluoridation and its discontinuation on fluoride content in the alveolar portion of the mandible in rats. Drinking water with three different fluoride contents (0, 50, 100 ppmF) was given to rats for three different periods (4, 13 and 25 weeks). Fluoride concentrations were measured in the crest, the middle, and the apical parts of the alveolar bone and in the body of the mandible. Furthermore, after fluoridated drinking water was given to rats for 4 or 13 weeks, distilled water was given to them for 21 or 12 weeks respectively; and the effect of the discontinuation on fluoride profiles was investigated. Layer samples were analyzed by abrasive microsampling. Fluoride and phosphorus concentrations were determined by ion-specific electrode and colorimetric procedures, respectively. There was an increase in fluoride concentrations in the mandible in proportion to the fluoride content in the drinking water and the duration of fluoridation. After fluoridation was discontinued, fluoride concentrations in the surface layers of the mandible presented a decrease. Among the four different parts of the mandible, the upper part of the alveolar bone and the alveolar crest part presented the highest rates of reduction. The relative reduction rate of fluoride concentration was closely related to the duration of discontinuation. The alveolar crest was affected most by the discontinuation of fluoridation, presenting the greatest reduction.

Fluoride barriers in Nb/Pb Josephson junctions

NASA Astrophysics Data System (ADS)

Asano, H.; Tanabe, K.; Michikami, O.; Igarashi, M.; Beasley, M. R.

1985-03-01

Josephson tunnel junctions are fabricated using a new class of artificial barriers, metal fluorides (Al fluoride and Zr fluoride). These fluoride barriers are deposited on the surface of a Nb base electrode, which are previously cleaned using a CF4 cleaning process, and covered by a Pb counterelectrode. The junctions with both Al fluoride and Zr fluoride barriers exhibit good tunneling characteristics and have low specific capacitance. In the case of Zr fluoride, it is observed that reasonable resistances are obtained even at thickness greater than 100 A. This phenomenon might be explained by tunneling via localized states in Zr fluoride.

Eukaryotic resistance to fluoride toxicity mediated by a widespread family of fluoride export proteins.

PubMed

Li, Sanshu; Smith, Kathryn D; Davis, Jared H; Gordon, Patricia B; Breaker, Ronald R; Strobel, Scott A

2013-11-19

Fluorine is an abundant element and is toxic to organisms from bacteria to humans, but the mechanisms by which eukaryotes resist fluoride toxicity are unknown. The Escherichia coli gene crcB was recently shown to be regulated by a fluoride-responsive riboswitch, implicating it in fluoride response. There are >8,000 crcB homologs across all domains of life, indicating that it has an important role in biology. Here we demonstrate that eukaryotic homologs [renamed FEX (fluoride exporter)] function in fluoride export. FEX KOs in three eukaryotic model organisms, Neurospora crassa, Saccharomyces cerevisiae, and Candida albicans, are highly sensitized to fluoride (>200-fold) but not to other halides. Some of these KO strains are unable to grow in fluoride concentrations found in tap water. Using the radioactive isotope of fluoride, (18)F, we developed an assay to measure the intracellular fluoride concentration and show that the FEX deletion strains accumulate fluoride in excess of the external concentration, providing direct evidence of FEX function in fluoride efflux. In addition, they are more sensitive to lower pH in the presence of fluoride. These results demonstrate that eukaryotic FEX genes encode a previously unrecognized class of fluoride exporter necessary for survival in standard environmental conditions.

Eukaryotic resistance to fluoride toxicity mediated by a widespread family of fluoride export proteins

PubMed Central

Li, Sanshu; Smith, Kathryn D.; Davis, Jared H.; Gordon, Patricia B.; Breaker, Ronald R.; Strobel, Scott A.

2013-01-01

Fluorine is an abundant element and is toxic to organisms from bacteria to humans, but the mechanisms by which eukaryotes resist fluoride toxicity are unknown. The Escherichia coli gene crcB was recently shown to be regulated by a fluoride-responsive riboswitch, implicating it in fluoride response. There are >8,000 crcB homologs across all domains of life, indicating that it has an important role in biology. Here we demonstrate that eukaryotic homologs [renamed FEX (fluoride exporter)] function in fluoride export. FEX KOs in three eukaryotic model organisms, Neurospora crassa, Saccharomyces cerevisiae, and Candida albicans, are highly sensitized to fluoride (>200-fold) but not to other halides. Some of these KO strains are unable to grow in fluoride concentrations found in tap water. Using the radioactive isotope of fluoride, 18F, we developed an assay to measure the intracellular fluoride concentration and show that the FEX deletion strains accumulate fluoride in excess of the external concentration, providing direct evidence of FEX function in fluoride efflux. In addition, they are more sensitive to lower pH in the presence of fluoride. These results demonstrate that eukaryotic FEX genes encode a previously unrecognized class of fluoride exporter necessary for survival in standard environmental conditions. PMID:24173035

Fluoride metabolism when added to salt.

PubMed

Whitford, Gary M

2005-01-01

The purpose of this review is to present the general characteristics of the metabolism of fluoride particularly as it occurs when ingested with fluoridated salt. Following the absorption of salt-borne fluoride from the stomach and intestines, its metabolism is identical to that of water-borne fluoride or other vehicles containing ionized fluoride. Because fluoridated salt is almost always ingested with food, however, absorption from the gastrointestinal tract may be delayed or reduced. Reports dealing with this subject have shown that fluoride absorption is delayed and, therefore, peak plasma concentrations are lower than when fluoride is ingested with water. The amount of ingested fluoride that is finally absorbed, however, is not appreciably affected unless the meal is composed mainly of components with high calcium concentrations. In this case, the extent of absorption can be reduced by as much as 50%. Fluoridated salt is also ingested less frequently than fluoridated water. Data are presented to show that the dose size and frequency of ingestion have only minor effects on fluoride retention in the body and on the concentrations in plasma, bone and enamel. Finally, calculations are presented to show that the risk of acute toxicity from fluoridated salt is virtually non-existent.

Fluoride content of still bottled water in Australia.

PubMed

Cochrane, N J; Saranathan, S; Morgan, M V; Dashper, S G

2006-09-01

Recently there has been a considerable increase in the consumption of bottled water in Australia. Overseas studies have found the fluoride levels in many bottled waters are well below levels considered optimal for preventing dental caries. This raises the concern that if bottled water is regularly consumed an effective means of preventing dental caries is unavailable. The aim of this study was to determine the fluoride concentration in 10 popular brands of still bottled water currently sold in Australia. The fluoride content of water samples were determined using an ion analyser and compared to a fluoride standard. The fluoride concentration of all bottled waters was less than 0.08 ppm. Only three of the 10 brands indicated the fluoride content on their labels. Melbourne reticulated water was found to be fluoridated at 1.02 ppm. All bottled waters tested contained negligible fluoride which justifies the concern that regular consumption of bottled water may reduce the benefits gained from water fluoridation. It is recommended that all bottled water companies should consider stating their fluoride content on their labels. This will inform consumers and dental care providers of the levels of fluoride in bottled water and allow an informed decision regarding consumption of fluoridated versus non-fluoridated drinking water.

Health Effects Associated with Water Fluoridation.

ERIC Educational Resources Information Center

Richmond, Virginia L.

1979-01-01

Discussion is presented concerning fluoridation of water supplies. Correlation between fluoride in drinking water and improved dental health is reviewed. Relationship is expressed between fluoridation and reduced tooth decay. Use of fluoride in treating skeletal disorders is discussed. Author advocates fluoridating water supplies. (SA)

Recovery of Uranium from Seawater: Preparation and Development of Polymer-Supported Extractants

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

Spiro, Alexandratos

2013-12-01

A new series of polymer-supported extractants is proposed for the removal and recovery of uranium from seawater. The objective is to produce polymers with improved stability, loading capacity, and sorption kinetics compared to what is found with amidoximes. The target ligands are diphosphonates and aminomethyldiphosphonates. Small molecule analogues, especially of aminomethyldiphos-phonates, have exceptionally high stability constants for the uranyl ion. The polymeric diphosphonates will have high affinities due to their ability to form six-membered rings with the uranyl ion while the aminomethyldiphosphonates may have yet higher affinities due to possible tridentate coordination and their greater acidity. A representative set ofmore » the polymers to be prepared are indicated.« less

PROCESS OF PREPARING URANIUM-IMPREGNATED GRAPHITE BODY

DOEpatents

Kanter, M.A.

1958-05-20

A method for the fabrication of graphite bodies containing uniformly distributed uranium is described. It consists of impregnating a body of graphite having uniform porosity and low density with an aqueous solution of uranyl nitrate hexahydrate preferably by a vacuum technique, thereafter removing excess aqueous solution from the surface of the graphite, then removing the solvent water from the body under substantially normal atmospheric conditions of temperature and pressure in the presence of a stream of dry inert gas, and finally heating the dry impregnated graphite body in the presence of inert gas at a temperature between 800 and 1400 d C to convert the uranyl nitrate hexahydrate to an oxide of uranium.

Absorption, distribution and excretion of inhaled hydrogen fluoride in the rat

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

Morris, J.B.

1979-01-01

Rats were subjected to whole body HF exposure for 6 hrs or to nose-only HF exposure for 1 hr. Total and/or ionic fluoride concentrations in selected tissues were determined at various times following exposure. In rats sacrificed 6 hrs after whole body exposure, dose-dependent increases in lung, plasma, and kidney total and ionic fluoride concentration occurred. Rats excreted more fluoride in the urine after whole body exposure than could be explained by the amount of HF inhaled. Considerable evidence suggests that airborne HF deposits on fur and is then ingested due to preening activity. Urinary fluoride excretion was increased bymore » nose-only exposure. The urinary fluoride excretion accounted for approximately twice the fluoride estimated to be inhaled during exposure. Tissue fluoride concentrations were elevated immediately after nose-only exposure. Fluoride concentrations in lung and kidney returned to control levels within 12 hrs. Plasma fluoride concentration was slightly elevated 24 hrs after the start of the 1 hr exposure but was at control levels at 96 hrs. Immediately following nose-only exposure, lung ionic fluoride concentrations were less than plasma ionic fluoride concentrations suggesting that the fluoride in the lung had reached that site via plasma transport rather than by inhalation. A dose-dependent increase in plasma ionic fluoride concentration occurred after upper respiratory tract HF exposure providing strong evidence that fluoride is absorbed systemically from that site. The plasma ionic fluoride concentration after upper respiratory tract exposure was of sufficient magnitude to account for the plasma fluoride concentrations observed in intact nose-only exposed rats. (ERB)« less

Exposure to water fluoridation and caries increment.

PubMed

Spencer, A J; Armfield, J M; Slade, G D

2008-03-01

The objective of this cohort study was to examine the association between exposure to water fluoridation and the increment of dental caries in two Australian states: Queensland (Qld)--5 per cent fluoridation coverage; and South Australia (SA)--70 per cent fluoridation coverage. Stratified random samples were drawn from fluoridated Adelaide and the largely non-fluoridated rest-of-state in SA, and fluoridated Townsville and non-fluoridated Brisbane in Qld. Children were enrolled between 1991 and 1992 (SA: 5-15 yrs old, n = 9,980; Qld: 5-12 yrs old, n = 10,695). Follow-up caries status data for 3 years (+/- 1/2 year) were available on 8,183 children in SA and 6,711 children in Qld. Baseline data on lifetime exposure to fluoridated water, use of other fluorides and socio-economic status (SES) were collected by questionnaire, and tooth surface caries status by dental examinations in school dental service clinics. Higher per cent lifetime exposure to fluoridated water (6 categories: 0;1-24; 25-49; 50-74; 75-99; 100 per cent) was a significant predictor (ANOVA, p < 0.01) of lower annualised Net Caries Increment (NCI) for the deciduous dentition in SA and Qld, but only for Qld in the permanent dentition. These associations persisted in multiple linear regression analyses controlling for age, gender, exposure to other fluorides and SES (p < 0.05). Water fluoridation was effective in reducing caries increment, even in the presence of a dilution effect from other fluorides. The effect of fluoridated water consumption was strongest in the deciduous dentition and where diffusion of food and beverages from fluoridated to non-fluoridated areas was less likely.

Physiologic Conditions Affect Toxicity of Ingested Industrial Fluoride

PubMed Central

Sauerheber, Richard

2013-01-01

The effects of calcium ion and broad pH ranges on free fluoride ion aqueous concentrations were measured directly and computed theoretically. Solubility calculations indicate that blood fluoride concentrations that occur in lethal poisonings would decrease calcium below prevailing levels. Acute lethal poisoning and also many of the chronic effects of fluoride involve alterations in the chemical activity of calcium by the fluoride ion. Natural calcium fluoride with low solubility and toxicity from ingestion is distinct from fully soluble toxic industrial fluorides. The toxicity of fluoride is determined by environmental conditions and the positive cations present. At a pH typical of gastric juice, fluoride is largely protonated as hydrofluoric acid HF. Industrial fluoride ingested from treated water enters saliva at levels too low to affect dental caries. Blood levels during lifelong consumption can harm heart, bone, brain, and even developing teeth enamel. The widespread policy known as water fluoridation is discussed in light of these findings. PMID:23840230

Physiologic conditions affect toxicity of ingested industrial fluoride.

PubMed

Sauerheber, Richard

2013-01-01

The effects of calcium ion and broad pH ranges on free fluoride ion aqueous concentrations were measured directly and computed theoretically. Solubility calculations indicate that blood fluoride concentrations that occur in lethal poisonings would decrease calcium below prevailing levels. Acute lethal poisoning and also many of the chronic effects of fluoride involve alterations in the chemical activity of calcium by the fluoride ion. Natural calcium fluoride with low solubility and toxicity from ingestion is distinct from fully soluble toxic industrial fluorides. The toxicity of fluoride is determined by environmental conditions and the positive cations present. At a pH typical of gastric juice, fluoride is largely protonated as hydrofluoric acid HF. Industrial fluoride ingested from treated water enters saliva at levels too low to affect dental caries. Blood levels during lifelong consumption can harm heart, bone, brain, and even developing teeth enamel. The widespread policy known as water fluoridation is discussed in light of these findings.

21 CFR 177.2510 - Polyvinylidene fluoride resins.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Polyvinylidene fluoride resins. 177.2510 Section... Repeated Use § 177.2510 Polyvinylidene fluoride resins. Polyvinylidene fluoride resins may be safely used... fluoride resins consist of basic resins produced by the polymerization of vinylidene fluoride. (b) The...

Comparison of in vitro fluoride uptake from whitening toothpastes and a conventional toothpaste in demineralised enamel.

PubMed

Altenburger, Markus J; Bernhart, Jasmin; Schicha, Thurid D; Wrbas, Karl-Thomas; Hellwig, Elmar

2010-01-01

Studies on the compatibility of abrasives and fluoride compounds deal exclusively with fluoride uptake and remineralization after storing the enamel specimens in a toothpaste-saliva mixture. The influence of brushing on the fluoride uptake when highly abrasive toothpastes are used has hardly been investigated so far. The aim of the present study was to investigate fluoride uptake in initially demineralised dental enamel after storage in, or brushing with, whitening toothpaste slurries, compared to a conventional toothpaste. For this purpose two widely available whitening toothpastes with ionically bound fluoride (sodium fluoride NaF), two with covalently-bound fluoride toothpastes (sodium monofluorophosphate, NaMFP) and a conventional amine fluoride toothpaste (AmF) were compared. The fluoride uptake after use of the AmF toothpaste was shown to be statistically significantly higher than that after application of the NaF toothpastes, which in turn was statistically significantly higher than the uptake resulting from NaMFP application. The fluoride uptake was slightly higher when the enamel samples were brushed with NaF toothpaste, rather than just stored in the respective toothpaste slurry. Brushing with highly abrasive toothpastes did not negatively influence fluoride uptake in demineralised dental enamel. The ionic form of the fluoride in toothpastes appears to be critical for increased fluoride uptake. The acidic components of the AmF toothpaste improved fluoride uptake compared to alkaline NaF toothpastes.

The effective use of fluorides in public health.

PubMed Central

Jones, Sheila; Burt, Brian A.; Petersen, Poul Erik; Lennon, Michael A.

2005-01-01

Dental caries remain a public health problem for many developing countries and for underprivileged populations in developed countries. This paper outlines the historical development of public health approaches to the use of fluoride and comments on their effectiveness. Early research and development was concerned with waterborne fluorides, both naturally occurring and added, and their effects on the prevalence and incidence of dental caries and dental fluorosis. In the latter half of the 20th century, the focus of research was on fluoride toothpastes and mouth rinses. More recently, systematic reviews summarizing these extensive databases have indicated that water fluoridation and fluoride toothpastes both substantially reduce the prevalence and incidence of dental caries. We present four case studies that illustrate the use of fluoride in modern public health practice, focusing on: recent water fluoridation schemes in California, USA; salt fluoridation in Jamaica; milk fluoridation in Chile; and the development of "affordable" fluoride toothpastes in Indonesia. Common themes are the concern to reduce demands for compliance with fluoride regimes that rely upon action by individuals and their families, and the issue of cost. We recommend that a community should use no more than one systemic fluoride (i.e. water or salt or milk fluoridation) combined with the use of fluoride toothpastes, and that the prevalence of dental fluorosis should be monitored in order to detect increases in or higher-than-acceptable levels. PMID:16211158

Solid state electrochemical current source

DOEpatents

Potanin, Alexander Arkadyevich; Vedeneev, Nikolai Ivanovich

2002-04-30

A cathode and a solid state electrochemical cell comprising said cathode, a solid anode and solid fluoride ion conducting electrolyte. The cathode comprises a metal oxide and a compound fluoride containing at least two metals with different valences. Representative compound fluorides include solid solutions of bismuth fluoride and potassium fluoride; and lead fluoride and potassium fluoride. Representative metal oxides include copper oxide, lead oxide, manganese oxide, vanadium oxide and silver oxide.

76 FR 37129 - Determination That SODIUM FLUORIDE F 18 (Sodium Fluoride F-18) Injection, 10 to 200 Millicuries...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-06-24

...] Determination That SODIUM FLUORIDE F 18 (Sodium Fluoride F-18) Injection, 10 to 200 Millicuries per Milliliter... FLUORIDE F 18 (sodium fluoride F-18) injection, 10 to 200 millicuries per milliliter (mCi/mL), was not... abbreviated new drug applications (ANDAs) for SODIUM FLUORIDE F 18 injection, 10 to 200 mCi/mL, if all other...

Process for converting magnesium fluoride to calcium fluoride

DOEpatents

Kreuzmann, A.B.; Palmer, D.A.

1984-12-21

This invention is a process for the conversion of magnesium fluoride to calcium fluoride whereby magnesium fluoride is decomposed by heating in the presence of calcium carbonate, calcium oxide or calcium hydroxide. Magnesium fluoride is a by-product of the reduction of uranium tetrafluoride to form uranium metal and has no known commercial use, thus its production creates a significant storage problem. The advantage of this invention is that the quality of calcium fluoride produced is sufficient to be used in the industrial manufacture of anhydrous hydrogen fluoride, steel mill flux or ceramic applications.

Health effects of groundwater fluoride contamination.

PubMed

Nayak, Bishwajit; Roy, Madan Mohan; Das, Bhaskar; Pal, Arup; Sengupta, Mrinal Kumar; De, Shankar Prasad; Chakraborti, Dipankar

2009-04-01

The people in Berhait block, Sahibganj district, Jharkhand state, India, have been exposed chronically to fluoridecontaminated groundwater. Hereby, we report the clinical effects of chronic exposure to fluoride. The study population was a convenience sample of 342 adults and 258 children living in the affected area. All volunteers filled out questionnaires and were examined. Well water from the six affected villages and urine samples were analyzed for fluoride using an ion-sensitive electrode. Twenty nine percent of 89 well water samples had fluoride concentrations above the Indian permissible limit of fluoride in drinking water. Eighty-five children and 72 adults had clinical fluorosis. Urine fluoride concentrations in children were 0.758-2.88 mg/L whereas in adults they were 0.331-10.36 mg/L. Clinical effects of fluoride included abnormal tooth enamel in children; adults had joint pain and deformity of the limbs and spine, along with ligamentous calcifications and exostosis formations in seven patients. Elevated urine fluoride concentrations supported the clinical diagnosis of fluorosis. Owing to insufficient fluoride-safe wells and lack of awareness of the danger of fluoride toxicity, villagers often drink fluoride-contaminated water. Villagers of Berhait block, including children, are at risk from chronic fluoride toxicity. To combat the situation, villagers need fluoride-safe water, education, and awareness of the danger about fluoride toxicity.

Uranium Biominerals Precipitated by an Environmental Isolate of Serratia under Anaerobic Conditions.

PubMed

Newsome, Laura; Morris, Katherine; Lloyd, Jonathan R

2015-01-01

Stimulating the microbially-mediated precipitation of uranium biominerals may be used to treat groundwater contamination at nuclear sites. The majority of studies to date have focussed on the reductive precipitation of uranium as U(IV) by U(VI)- and Fe(III)-reducing bacteria such as Geobacter and Shewanella species, although other mechanisms of uranium removal from solution can occur, including the precipitation of uranyl phosphates via bacterial phosphatase activity. Here we present the results of uranium biomineralisation experiments using an isolate of Serratia obtained from a sediment sample representative of the Sellafield nuclear site, UK. When supplied with glycerol phosphate, this Serratia strain was able to precipitate 1 mM of soluble U(VI) as uranyl phosphate minerals from the autunite group, under anaerobic and fermentative conditions. Under phosphate-limited anaerobic conditions and with glycerol as the electron donor, non-growing Serratia cells could precipitate 0.5 mM of uranium supplied as soluble U(VI), via reduction to nano-crystalline U(IV) uraninite. Some evidence for the reduction of solid phase uranyl(VI) phosphate was also observed. This study highlights the potential for Serratia and related species to play a role in the bioremediation of uranium contamination, via a range of different metabolic pathways, dependent on culturing or in situ conditions.

Uranium Biominerals Precipitated by an Environmental Isolate of Serratia under Anaerobic Conditions

PubMed Central

Newsome, Laura; Morris, Katherine; Lloyd, Jonathan. R.

2015-01-01

Stimulating the microbially-mediated precipitation of uranium biominerals may be used to treat groundwater contamination at nuclear sites. The majority of studies to date have focussed on the reductive precipitation of uranium as U(IV) by U(VI)- and Fe(III)-reducing bacteria such as Geobacter and Shewanella species, although other mechanisms of uranium removal from solution can occur, including the precipitation of uranyl phosphates via bacterial phosphatase activity. Here we present the results of uranium biomineralisation experiments using an isolate of Serratia obtained from a sediment sample representative of the Sellafield nuclear site, UK. When supplied with glycerol phosphate, this Serratia strain was able to precipitate 1 mM of soluble U(VI) as uranyl phosphate minerals from the autunite group, under anaerobic and fermentative conditions. Under phosphate-limited anaerobic conditions and with glycerol as the electron donor, non-growing Serratia cells could precipitate 0.5 mM of uranium supplied as soluble U(VI), via reduction to nano-crystalline U(IV) uraninite. Some evidence for the reduction of solid phase uranyl(VI) phosphate was also observed. This study highlights the potential for Serratia and related species to play a role in the bioremediation of uranium contamination, via a range of different metabolic pathways, dependent on culturing or in situ conditions. PMID:26132209

Probing the Oxygen Environment in UO22+ by Solid-State O-17 Nuclear Magnetic Resonance Spectroscopy and Relativistic Density Functional Calculations

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

Cho, Herman M.; De Jong, Wibe A.; Soderquist, Chuck Z.

A combined theoretical and solid-state O-17 NMR study of the electronic structure of the uranyl ion UO22+ in (NH4)4UO2(CO3)3 and rutherfordine UO2CO3 is presented, the former representing a system with a hydrogen-bonding environment around the uranyl oxygens, and the latter exemplifying a uranyl environment without hydrogens. A fully relativistic ab initio treatment reveals unique features of the U-O covalent bond, including the finding of O-17 chemical shift anisotropies that are among the largest ever reported (>1200 ppm). Computational results for the oxygen electric field gradient tensor are found to be consistently larger in magnitude than experimental solid-state O-17 NMR measurementsmore » in a 7.05 T magnetic field indicate. A modified version of the Solomon theory of the two-spin echo amplitude for a spin-5/2 nucleus is developed and applied to the analysis of the O-17 echo signal of UO22+. The William R. Wiley environmental Molecular Sciences Laboratory is a US Department of Energy national scientific user facility located at Pacific Northwest National Laboratory (PNNL) in Richland, Washington. PNNL is operated by Battelle for the US Department of Energy.« less

Synthesis and structure determination of uranyl peroxide nanospheres in the presence of organic structure directing agents

NASA Astrophysics Data System (ADS)

Forbes, T. Z.; Burns, P. C.

2007-12-01

Recently, actinyl peroxide nanoclusters containing 20, 24, 28, or 32 actinyl polyhedra have been synthesized and their structures identified with single crystal X-ray diffraction [1]. Most nanomaterials are composed of main group elements or transition metals, therefore, these actinyl nanospheres may display vastly different chemical and physical properties due to the presence of filled f-orbitals. A major goal of our research group is to create novel actinyl materials, focusing on nano- and mesoporous materials. The original nanosphere syntheses were limited to inorganic crystallization agents, such as monovalent cations. Over the last decade, the use of organic compounds and surfactants have received increased attention as structure-directing agents for the generation of novel inorganic materials. Using structure-directing organic amines we have successfully synthesized and determined the structures of uranyl nanospheres containing 40 and 50 uranyl polyhedra. The topology of the skeletal U-50 nanosphere is identical to the C50Cl10 fullerene [2]. The topographical relationship between the actinyl nanospheres and fullerene or fullerene-like material may provide additional insight into stable configurations for lower fullerenes. [1] Burns et al., Actinyl peroxide nanospheres. Angewandte Chemie, International Edition, 2005. 44(14): p. 2135. [2] Xie et al., Capturing the Labile Fullerene[50] as C50Cl10. Science, (2004) 305(5671): p. 699.

Establishing the traceability of a uranyl nitrate solution to a standard reference material

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

Jackson, C.H.; Clark, J.P.

1978-01-01

A uranyl nitrate solution for use as a Working Calibration and Test Material (WCTM) was characterized, using a statistically designed procedure to document traceability to National Bureau of Standards Reference Material (SPM-960). A Reference Calibration and Test Material (PCTM) was prepared from SRM-960 uranium metal to approximate the acid and uranium concentration of the WCTM. This solution was used in the characterization procedure. Details of preparing, handling, and packaging these solutions are covered. Two outside laboratories, each having measurement expertise using a different analytical method, were selected to measure both solutions according to the procedure for characterizing the WCTM. Twomore » different methods were also used for the in-house characterization work. All analytical results were tested for statistical agreement before the WCTM concentration and limit of error values were calculated. A concentration value was determined with a relative limit of error (RLE) of approximately 0.03% which was better than the target RLE of 0.08%. The use of this working material eliminates the expense of using SRMs to fulfill traceability requirements for uranium measurements on this type material. Several years' supply of uranyl nitrate solution with NBS traceability was produced. The cost of this material was less than 10% of an equal quantity of SRM-960 uranium metal.« less

Appropriate uses of fluorides for children: guidelines from the Canadian Workshop on the Evaluation of Current Recommendations Concerning Fluorides.

PubMed Central

Clark, D C

1993-01-01

OBJECTIVE: To prevent fluorosis caused by excessive fluoride ingestion by revising recommendations for fluoride intake by children. OPTIONS: Limiting fluoride ingestion from fluoridated water, fluoride supplements and fluoride dentifrices. OUTCOMES: Reduction in the prevalence of dental fluorosis and continued prevention of dental caries. EVIDENCE: Before the workshop, experts prepared comprehensive literature reviews of fluoride therapies, fluoride ingestion and the prevalence and causes of dental fluorosis. The papers, which were peer-reviewed, revised and circulated to the workshop participants, formed the basis of the workshop discussions. VALUES: Recommendations to limit fluoride intake were vigorously debated before being adopted as the consensus opinion of the workshop group. BENEFITS, HARMS AND COSTS: Decrease in the prevalence of dental fluorosis with continuing preventive effects of fluoride use. The only significant cost would be in preparing new, low-concentration fluoride products for distribution. RECOMMENDATIONS: Fluoride supplementation should be limited to children 3 years of age and older in areas where there is less than 0.3 ppm of fluoride in the water supply. Children in all areas should use only a "pea-sized" amount of fluoride dentifrice no more than twice daily under the supervision of an adult. VALIDATION: These recommendations are almost identical to changes to recommendations for the use of fluoride supplements recently proposed by a group of European countries. SPONSORS: The workshop was organized by Dr. D. Christopher Clark, of the University of British Columbia, and Drs. Hardy Limeback and Ralph C. Burgess, of the University of Toronto, and funded by Proctor and Gamble Inc., Toronto, the Medical Research Council of Canada and Health Canada (formerly the Department of National Health and Welfare). The recommendations were formally adopted by the Canadian Dental Association in April 1993. PMID:8261348

Review on fluoride-releasing restorative materials--fluoride release and uptake characteristics, antibacterial activity and influence on caries formation.

PubMed

Wiegand, Annette; Buchalla, Wolfgang; Attin, Thomas

2007-03-01

The purpose of this article was to review the fluoride release and recharge capabilities, and antibacterial properties, of fluoride-releasing dental restoratives, and discuss the current status concerning the prevention or inhibition of caries development and progression. Information from original scientific full papers or reviews listed in PubMed (search term: fluoride release AND (restorative OR glass-ionomer OR compomer OR polyacid-modified composite resin OR composite OR amalgam)), published from 1980 to 2004, was included in the review. Papers dealing with endodontic or orthodontic topics were not taken into consideration. Clinical studies concerning secondary caries development were only included when performed in split-mouth design with an observation period of at least three years. Fluoride-containing dental materials show clear differences in the fluoride release and uptake characteristics. Short- and long-term fluoride releases from restoratives are related to their matrices, setting mechanisms and fluoride content and depend on several environmental conditions. Fluoride-releasing materials may act as a fluoride reservoir and may increase the fluoride level in saliva, plaque and dental hard tissues. However, clinical studies exhibited conflicting data as to whether or not these materials significantly prevent or inhibit secondary caries and affect the growth of caries-associated bacteria compared to non-fluoridated restoratives. Fluoride release and uptake characteristics depend on the matrices, fillers and fluoride content as well as on the setting mechanisms and environmental conditions of the restoratives. Fluoride-releasing materials, predominantly glass-ionomers and compomers, did show cariostatic properties and may affect bacterial metabolism under simulated cariogenic conditions in vitro. However, it is not proven by prospective clinical studies whether the incidence of secondary caries can be significantly reduced by the fluoride release of restorative materials.

Streptozotocin Aggravated Osteopathology and Insulin Induced Osteogenesis Through Co-treatment with Fluoride.

PubMed

Yang, Chen; Zhang, Mengmeng; Li, Yagang; Wang, Yan; Mao, Weixian; Gao, Yuan; Xu, Hui

2015-12-01

The role of insulin in the mechanism underlying the excessive fluoride that causes skeletal lesion was studied. The in vitro bone marrow stem cells (BMSC) collected from Kunming mice were exposed to varying concentrations of fluoride with or without insulin. The cell viability and early differentiation of BMSC co-treated with fluoride and insulin were measured by using cell counting kit-8 and Gomori modified calcium-cobalt method, respectively. We further investigated the in vivo effects of varying dose of fluoride on rats co-treated with streptozotocin (STZ). Wistar rats were divided into six groups which included normal control, 10 mg fluoride/kg day group, 20 mg fluoride/kg day group, STZ control, STZ+10 mg fluoride/kg day group, and STZ+20 mg fluoride/kg day group. The rats were administered with sodium fluoride (NaF) by gavage with water at doses 10 and 20 mg fluoride/kg day for 2 months. In a period of one month, half of rats in every group were treated with streptozotocin (STZ) once through intraperitoneal injection at 52 mg/kg body weight. The serum glucose, HbA1c, and insulin were determined. Bone mineral content and insulin release were assessed. The results showed insulin combined with fluoride stimulated BMSC cell viability in vitro. The bone mineral content reduced in rats treated with higher dose of fluoride and decreased immensely in rat co-treated with fluoride and STZ. Similarly, a combination treatment of a high dose of fluoride and STZ decreased insulin sensitivity and activity. To sum up, these data indicated fluoride influenced insulin release, activity, and sensitivity. Furthermore, the insulin state in vivo interfered in the osteogenesis in turn and implied there was a close relation between insulin and bone pathogenesis in the mechanism of fluoride toxicity.

FLUORIDE: A REVIEW OF USE AND EFFECTS ON HEALTH.

PubMed

Kanduti, Domen; Sterbenk, Petra; Artnik, Barbara

2016-04-01

Appropriate oral health care is fundamental for any individual's health. Dental caries is still one of the major public health problems. The most effective way of caries prevention is the use of fluoride. The aim of our research was to review the literature about fluoride toxicity and to inform physicians, dentists and public health specialists whether fluoride use is expedient and safe. Data we used in our review were systematically searched and collected from web pages and documents published from different international institutions. Fluoride occurs naturally in our environment but we consume it in small amounts. Exposure can occur through dietary intake, respiration and fluoride supplements. The most important factor for fluoride presence in alimentation is fluoridated water. Methods, which led to greater fluoride exposure and lowered caries prevalence, are considered to be one of the greatest accomplishments in the 20th century`s public dental health. During pregnancy, the placenta acts as a barrier. The fluoride, therefore, crosses the placenta in low concentrations. Fluoride can be transmitted through the plasma into the mother's milk; however, the concentration is low. The most important action of fluoride is topical, when it is present in the saliva in the appropriate concentration. The most important effect of fluoride on caries incidence is through its role in the process of remineralization and demineralization of tooth enamel. Acute toxicity can occur after ingesting one or more doses of fluoride over a short time period which then leads to poisoning. Today, poisoning is mainly due to unsupervised ingestion of products for dental and oral hygiene and over-fluoridated water. Even though fluoride can be toxic in extremely high concentrations, it`s topical use is safe. The European Academy of Paediatric Dentistry (EAPD) recommends a preventive topical use of fluoride supplements because of their cariostatic effect.

FLUORIDE CONTENT OF COMMERCIALLY AVAILABLE BOTTLED DRINKING WATER IN BANGKOK, THAILAND.

PubMed

Rirattanapong, Praphasri; Rirattanapong, Opas

2016-09-01

The use of bottled drinking water may be a source of fluoride and could be a risk factor for fluorosis among infants and young children. The aim of this study was to evaluate the fluoride content of commercially available bottled drinking water in Bangkok, Thailand. Forty-five water samples (15 samples of plain water and 30 samples of mineral water) were purchased from several supermarkets in Bangkok, Thailand. Three bottles of each water sample were purchased, and the fluoride content of each sample was measured twice using a combination fluoride-ion selective electrode. The average reading for each sample was then calculated. Data were analyzed by descriptive statistics. Differences between mineral and plain water samples were determined by Student’s t-test. The mean (±SD) fluoride content for all the water samples was 0.17 (±0.17) mg F/l (range: 0.01-0.89 mg F/l). Six brands (13%) tested stated the fluoride content on the label. The actual fluoride content in each of their brands varied little from the label. Eight samples (18%) had a fluoride content >0.3 mg F/l and two samples (4%) had a fluoride content >0.6 mg F/l. The mean mineral water fluoride concentration was significantly higher than the mean fluoride concentration of plain water (p=0.001). We found commercially sold bottled drinking water in Bangkok, Thailand contained varying concentrations of fluoride; some with high concentrations of fluoride. Health professions need to be aware this varying fluoride content of bottled drinking water and educate the parents of infants and small children about this when prescribing fluoride supplements. Consideration should be made to have fluoride content put on the label of bottled water especially among brands with a content >0.3 mg F/l.

Evaluation of the direct and diffusion methods for the determination of fluoride content in table salt

PubMed Central

Martínez-Mier, E. Angeles; Soto-Rojas, Armando E.; Buckley, Christine M.; Margineda, Jorge; Zero, Domenick T.

2010-01-01

Objective The aim of this study was to assess methods currently used for analyzing fluoridated salt in order to identify the most useful method for this type of analysis. Basic research design Seventy-five fluoridated salt samples were obtained. Samples were analyzed for fluoride content, with and without pretreatment, using direct and diffusion methods. Element analysis was also conducted in selected samples. Fluoride was added to ultra pure NaCl and non-fluoridated commercial salt samples and Ca and Mg were added to fluoride samples in order to assess fluoride recoveries using modifications to the methods. Results Larger amounts of fluoride were found and recovered using diffusion than direct methods (96%–100% for diffusion vs. 67%–90% for direct). Statistically significant differences were obtained between direct and diffusion methods using different ion strength adjusters. Pretreatment methods reduced the amount of recovered fluoride. Determination of fluoride content was influenced both by the presence of NaCl and other ions in the salt. Conclusion Direct and diffusion techniques for analysis of fluoridated salt are suitable methods for fluoride analysis. The choice of method should depend on the purpose of the analysis. PMID:20088217

[Estimation of exposure to fluoride in "Los Altos de Jalisco", México].

PubMed

Hurtado-Jiménez, Roberto; Gardea-Torresdey, Jorge

2005-01-01

To estimate the level of fluoride exposure and human health risks in Los Altos de Jalisco (Jalisco State Heights) region. This study was conducted between May and July 2002. The fluoride concentrations of 105 water wells and six tap water samples were electrochemically measured. Exposure doses to fluoride and total intake of fluoride were estimated for babies (10 kg), children (20 kg), and adults (70 kg). The fluoride concentration of the water samples ranged from 0.1 to 17.7 mg/l. More than 45% of the water samples exceeded the national guideline value for fluoride of 1.5 mg/l. The estimated values of the exposure doses to fluoride and total intake of fluoride were in the range of 0.04-1.8 mg/kg/d and 0.5-18.4 mg/d, respectively. Dental fluorosis, skeletal fluorosis, and bone fractures are some of the potential health risks due to the intake of high doses of fluoride for the population of Los Altos de Jalisco. In order to reduce health risks, fluoridated salt,fluoridated toothpastes, and drinking water containing more than 0.7 mg/l of fluoride should be avoided.

Fluoride in the environment and its metabolism in humans.

PubMed

Jha, Sunil Kumar; Mishra, Vinay Kumar; Sharma, Dinesh Kumar; Damodaran, Thukkaram

2011-01-01

The presence of environmental fluoride and its impact on human health is well documented. When consumed in adequate quantity, fluoride prevents dental caries, assists in the formation of dental enamels, and prevents deficiencies in bone mineralization. At excessive exposure levels, ingestion of fluoride causes dental fluorosis skeletal fluorosis, and manifestations such as gastrointestinal, neurological, and urinary problems. The distribution of fluoride in the environment is uneven and largely is believed to derive from geogenic causes. The natural sources of fluoride are fluorite, fluorapatite, and cryolite, whereas anthropogenic sources include coal burning, oil refining, steel production, brick-making industries, and phosphatic fertilizer plants, among others. Among the various sources of fluoride in the environment, those of anthropogenic origin have occasionally been considered to be major ones. The gourndwater is more susceptible to fluoride accumulation and contamination than are other environmental media, primarily because of its contact with geological substrates underneath. The high fluoride concentration in water usually reflects the solubility of fluoride (CaF₂). High concentrations are also often associated with soft, alkaline, and calcium-deficient waters. The fluoride compounds that occur naturally in drinking water are almost totally bioavailable (90%) and are completely absorbed from the gastrointestinal tract. As a result, drinking water is considered to be the potential source of fluoride that causes fluorosis. Because the bioavailability of fluoride is generally reduced in humans when consumed with milk or a calcium-rich diet, it is highly recommended that the inhabitants of fluoride-contaminated areas should incorporate calcium-rich foods in their routine diet. Guidelines for limiting the fluoride intake from drinking water have been postulated by various authorities. Such limits are designed to protect public health and should reflect all fluoride intake sources, including dietary fluoride. The toxicological risks posed by fluoride could be better understood if epidemiological surveillance for dental and skeletal fluorosis would be systematically conducted in fluoride-affected areas. Such input would greatly improve understanding of the human dose-response relationship. Such surveillance of potentially high fluoride areas is also important because it would help to delineate, much earlier, the remedial measures that are appropriate for those areas.

Potential fluoride toxicity from oral medicaments: A review.

PubMed

Ullah, Rizwan; Zafar, Muhammad Sohail; Shahani, Nazish

2017-08-01

The beneficial effects of fluoride on human oral health are well studied. There are numerous studies demonstrating that a small amount of fluoride delivered to the oral cavity decreases the prevalence of dental decay and results in stronger teeth and bones. However, ingestion of fluoride more than the recommended limit leads to toxicity and adverse effects. In order to update our understanding of fluoride and its potential toxicity, we have described the mechanisms of fluoride metabolism, toxic effects, and management of fluoride toxicity. The main aim of this review is to highlight the potential adverse effects of fluoride overdose and poorly understood toxicity. In addition, the related clinical significance of fluoride overdose and toxicity has been discussed.

Thiocyanate complexes of uranium in multiple oxidation states: a combined structural, magnetic, spectroscopic, spectroelectrochemical, and theoretical study.

PubMed

Hashem, Emtithal; Platts, James A; Hartl, František; Lorusso, Giulia; Evangelisti, Marco; Schulzke, Carola; Baker, Robert J

2014-08-18

A comprehensive study of the complexes A4[U(NCS)8] (A = Cs, Et4N, (n)Bu4N) and A3[UO2(NCS)5] (A = Cs, Et4N) is described, with the crystal structures of [(n)Bu4N]4[U(NCS)8]·2MeCN and Cs3[UO2(NCS)5]·O0.5 reported. The magnetic properties of square antiprismatic Cs4[U(NCS)8] and cubic [Et4N]4[U(NCS)8] have been probed by SQUID magnetometry. The geometry has an important impact on the low-temperature magnetic moments: at 2 K, μeff = 1.21 μB and 0.53 μB, respectively. Electronic absorption and photoluminescence spectra of the uranium(IV) compounds have been measured. The redox chemistry of [Et4N]4[U(NCS)8] has been explored using IR and UV-vis spectroelectrochemical methods. Reversible 1-electron oxidation of one of the coordinated thiocyanate ligands occurs at +0.22 V vs Fc/Fc(+), followed by an irreversible oxidation to form dithiocyanogen (NCS)2 which upon back reduction regenerates thiocyanate anions coordinating to UO2(2+). NBO calculations agree with the experimental spectra, suggesting that the initial electron loss of [U(NCS)8](4-) is delocalized over all NCS(-) ligands. Reduction of the uranyl(VI) complex [Et4N]3[UO2(NCS)5] to uranyl(V) is accompanied by immediate disproportionation and has only been studied by DFT methods. The bonding in [An(NCS)8](4-) (An = Th, U) and [UO2(NCS)5](3-) has been explored by a combination of DFT and QTAIM analysis, and the U-N bonds are predominantly ionic, with the uranyl(V) species more ionic that the uranyl(VI) ion. Additionally, the U(IV)-NCS ion is more ionic than what was found for U(IV)-Cl complexes.

Perrhenate complexation by uranyl in traditional solvents and in ionic liquids: a joint molecular dynamics/spectroscopic study.

PubMed

Chaumont, Alain; Klimchuk, Olga; Gaillard, Clotilde; Billard, Isabelle; Ouadi, Ali; Hennig, Christoph; Wipff, Georges

2012-03-15

The complexation of perrhenate (ReO(4)(-)) anions by the uranyl (UO(2)(2+)) cation has been investigated by joint molecular dynamics simulations and spectroscopic (UV-vis, TRLFS, and EXAFS) studies in aqueous solution, acetonitrile, and three ionic liquids (ILs), namely, [Bmi][Tf(2)N], [Me(3)BuN][Tf(2)N], and [Bu(3)MeN][Tf(2)N] that are based on the same Tf(2)N(-) anion (bis(trifluoromethylsulfonyl)imide) and either Bmi(+) (1-butyl,3-methylimidazolium), Me(3)BuN(+), or Bu(3)MeN(+) cations. They show that ReO(4)(-) behaves as a weak ligand in aqueous solution and as a strong ligand in acetonitrile and in the ILs. According to MD simulations in aqueous solution, the UO(2)(ReO(4))(2) complex quickly dissociates to form UO(2)(H(2)O)(5)(2+), while in acetonitrile, a stable UO(2)(ReO(4))(5)(3-) species forms from dissociated ions. In the ILs, the UO(2)(ReO(4))(n)(2-n) complexes (n = 1 to 5) remained stable along the dynamics, and to assess their relative stabilities, we computed the free energy profiles for stepwise ReO(4)(-) complexation to uranyl. In the two studied ILs, complexation is favored, leading to the UO(2)(ReO(4))(5)(3-) species in [Bmi][Tf(2)N] and to UO(2)(ReO(4))(4)(2-) in [Bu(3)MeN][Tf(2)N]. Furthermore, in both acetonitrile and [Bmi][Tf(2)N] solutions, MD and PMF simulations support the formation of dimeric uranyl complexes [UO(2)(ReO(4))(4)](2)(4-) with two bridging ReO(4)(-) ligands. The simulation results are qualitatively consistent with spectroscopic observations in the different solvents, without firmly concluding, however, on the precise composition and structure of the complexes in the solutions. © 2012 American Chemical Society

Nuclear proliferomics: A new field of study to identify signatures of nuclear materials as demonstrated on alpha-UO3.

PubMed

Schwerdt, Ian J; Brenkmann, Alexandria; Martinson, Sean; Albrecht, Brent D; Heffernan, Sean; Klosterman, Michael R; Kirkham, Trenton; Tasdizen, Tolga; McDonald Iv, Luther W

2018-08-15

The use of a limited set of signatures in nuclear forensics and nuclear safeguards may reduce the discriminating power for identifying unknown nuclear materials, or for verifying processing at existing facilities. Nuclear proliferomics is a proposed new field of study that advocates for the acquisition of large databases of nuclear material properties from a variety of analytical techniques. As demonstrated on a common uranium trioxide polymorph, α-UO 3 , in this paper, nuclear proliferomics increases the ability to improve confidence in identifying the processing history of nuclear materials. Specifically, α-UO 3 was investigated from the calcination of unwashed uranyl peroxide at 350, 400, 450, 500, and 550 °C in air. Scanning electron microscopy (SEM) images were acquired of the surface morphology, and distinct qualitative differences are presented between unwashed and washed uranyl peroxide, as well as the calcination products from the unwashed uranyl peroxide at the investigated temperatures. Differential scanning calorimetry (DSC), UV-Vis spectrophotometry, powder X-ray diffraction (p-XRD), and thermogravimetric analysis-mass spectrometry (TGA-MS) were used to understand the source of these morphological differences as a function of calcination temperature. Additionally, the SEM images were manually segmented using Morphological Analysis for MAterials (MAMA) software to identify quantifiable differences in morphology for three different surface features present on the unwashed uranyl peroxide calcination products. No single quantifiable signature was sufficient to discern all calcination temperatures with a high degree of confidence; therefore, advanced statistical analysis was performed to allow the combination of a number of quantitative signatures, with their associated uncertainties, to allow for complete discernment by calcination history. Furthermore, machine learning was applied to the acquired SEM images to demonstrate automated discernment with at least 89% accuracy. Copyright © 2018 Elsevier B.V. All rights reserved.

Ions generated from uranyl nitrate solutions by electrospray ionization (ESI) and detected with Fourier transform ion-cyclotron resonance (FT-ICR) mass spectrometry.

PubMed

Pasilis, Sofie; Somogyi, Arpád; Herrmann, Kristin; Pemberton, Jeanne E

2006-02-01

Electrospray ionization (ESI) of uranyl nitrate solutions generates a wide variety of positively and negatively charged ions, including complex adducts of uranyl ions with methoxy, hydroxy, and nitrate ligands. In the positive ion mode, ions detected by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry are sensitive to instrumental tuning parameters such as quadrupole operating frequency and trapping time. Positive ions correspond to oligomeric uranyl nitrate species that can be characterized as having a general formula of [(UO(2))(n)(A)(m)(CH(3)OH)(s)](+) or [(UO(2))(n)(O)(A)(m)(CH(3)OH)(s)](+) with n = 1-4, m = 1-7, s = 0 or 1, and A = OH, NO(3), CH(3)O or a combination of these, although the formation of NO(3)-containing species is preferred. In the negative ion mode, complexes of the form [(UO(2))(NO(3))(m)](-) (m = 1-3) are detected, although the formation of the oxo-containing ions [(UO(2))(O)(n)(NO(3))(m)](-) (n = 1-2, m = 1-2) and the hydroxy-containing ions [(UO(2))(OH)(n)(NO(3))(m)](-) (n = 1-2, m = 0-1) are also observed. The extent of coordinative unsaturation of both positive and negative ions can be determined by ligand association/exchange and H/D exchange experiments using D(2)O and CD(3)OD as neutral reaction partners in the gas-phase. Positive ions are of varying stability and reactivity and may fragment extensively upon collision with D(2)O, CD(3)OD and N(2) in sustained off-resonance irradiation/collision-induced dissociation (SORI-CID) experiments. Electron-transfer reactions, presumably occurring during electrospray ionization but also in SORI-CID, can result in reduction of U(VI) to U(V) and perhaps even U(IV).

A spectroscopic study of uranyl speciation in chloride-bearing solutions at temperatures up to 250 °C

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

Migdisov, A. A.; Boukhalfa, H.; Timofeev, A.

The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO 2 2+, UO 2Cl +, and UO 2Cl 2°. UO 2Cl 3 - is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl-) number. Thermodynamic stability constants derived for these species showmore » fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO 2Cl 4 2- and UO 2Cl 5 3- contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T >150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO 2Cl 2°. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO 2 2+ + Cl - = UO 2Cl + are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO 2 2+ + 2Cl - = UO 2Cl 2° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.« less

A spectroscopic study of uranyl speciation in chloride-bearing solutions at temperatures up to 250 °C

DOE PAGES

Migdisov, A. A.; Boukhalfa, H.; Timofeev, A.; ...

2017-10-24

The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO 2 2+, UO 2Cl +, and UO 2Cl 2°. UO 2Cl 3 - is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl-) number. Thermodynamic stability constants derived for these species showmore » fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO 2Cl 4 2- and UO 2Cl 5 3- contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T >150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO 2Cl 2°. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO 2 2+ + Cl - = UO 2Cl + are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO 2 2+ + 2Cl - = UO 2Cl 2° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.« less

Uranyl carboxyphosphonates that incorporate Cd(II)

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

Alsobrook, Andrea N.; Alekseev, Evgeny V.; Depmeier, Wulf

2011-05-15

The hydrothermal treatment of UO{sub 3}, Cd(CH{sub 3}CO{sub 2}){sub 2}.2H{sub 2}O, and triethyl phosphonoacetate results in the formation of Cd{sub 2}[(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 3}O{sub 3}(OH)(H{sub 2}O){sub 2}].16H{sub 2}O (CdUPAA-1), [Cd{sub 3}(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 6}(H{sub 2}O){sub 13}].6H{sub 2}O (CdUPAA-2), and Cd(H{sub 2}O){sub 2}[(UO{sub 2})(PO{sub 3}CH{sub 2}CO{sub 2})(H{sub 2}O)]{sub 2} (CdUPAA-3). CdUPAA-1 adopts a cubic three-dimensional structure constructed from planar uranyl oxide clusters containing both UO{sub 7} pentagonal bipyramids and UO{sub 8} hexagonal bipyramids that are linked by Cd(II) cations and phosphonoacetate to yield large cavities approximately 16 A across that are filled with disordered watermore » molecules. CdUPAA-2 forms a rhombohedral three-dimensional channel structure that is assembled from UO{sub 7} pentagonal bipyramids that are bridged by phosphonoacetate. CdUPAA-3 is layered with the hydrated Cd(II) cations incorporated directly into the layers linking one-dimensional uranyl phosphonate substructures together. In this structure, there are complex networks of hydrogen bonds that exist within the sheets, and also stitch the sheets together. -- Graphical abstract: A view of part of the cubic structure of Cd{sub 2}[(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 3}O{sub 3}(OH)(H{sub 2}O){sub 2}].16H{sub 2}O. Display Omitted highlights: > High symmetry uranyl compounds. > Three-dimensional structures. > Porous materials. > Heterobimetallic compounds.« less

Incorporation mechanisms of actinide elements into the structures of U 6+ phases formed during the oxidation of spent nuclear fuel

NASA Astrophysics Data System (ADS)

Burns, Peter C.; Ewing, Rodney C.; Miller, Mark L.

1997-05-01

Uranyl oxide hydrate and uranyl silicate phases will form due to the corrosion and alteration of spent nuclear fuel under oxidizing conditions in silica-bearing solution. The actinide elements in the spent fuel may be incorporated into the structures of these secondary U6+ phases during the long-term corrosion of the UO 2 in spent fuel. The incorporation of actinide elements into the crystal structures of the alteration products may decrease actinide mobility. The crystal chemistry of the various oxidation states of the actinide elements of environmental concern is examined to identify possible incorporation mechanisms. The substitutions Pu 6+U 6+ and (Pu 5+, Np 5+)U 6+ should readily occur in many U 6+ structures, although structural modification may be required to satisfy local bond-valence requirements. Crystal-chemical characteristics of the U 6+ phases indicate that An 4+ (An: actinide)U 6+ substitution is likely to occur in the sheets of uranyl polyhedra that occur in the structures of the minerals schoepite, [(UO 2) 8O 2(OH) 12](H 2O) 12, ianthinite, [U 24+ (UO 2) 4O 6(OH) 4(H 2O) 4](H 2O) 5, becquerelite, Ca[(UO 2) 3O 2(OH) 3] 2(H 2O) 8, compreignacite, K 2[(UO 2) 3O 2(OH) 3] 2(H 2O) 8, α-uranophane, Ca[(UO 2)(SiO 3OH)] 2(H 2O) 5, and boltwoodite, K(H 2O)[(UO 2)(SiO 4)], all of which are likely to form due to the oxidation and alteration of the UO 2 in spent fuel. The incorporation of An 3+ into the sheets of the structures of α-uranophane and boltwoodite, as well as interlayer sites of various uranyl phases, may occur.

A spectroscopic study of uranyl speciation in chloride-bearing solutions at temperatures up to 250 °C

NASA Astrophysics Data System (ADS)

Migdisov, A. A.; Boukhalfa, H.; Timofeev, A.; Runde, W.; Roback, R.; Williams-Jones, A. E.

2018-02-01

The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO22+, UO2Cl+, and UO2Cl2°. UO2Cl3- is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl-) number. Thermodynamic stability constants derived for these species show fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO2Cl42- and UO2Cl53- contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T > 150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO2Cl2°. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO22+ + Cl- = UO2Cl+ are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO22+ + 2Cl- = UO2Cl2° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.

SEPARATION OF METAL VALUES FROM NUCLEAR REACTOR

DOEpatents

Campbell, D.O.; Cathers, G.I.

1962-06-19

A method is given for separating beryllium fluoride and an alkali metal fluoride from a mixture containing same and rare earth fluorides. The method comprises contacting said mixture with a liquid hydrogen fluoride solvent containing no more than about 30 per cent water by weight and saturated with a fluoride salt characterized by its solubility in anhydrous hydrogen fluoride for a period of time sufficient to dissolve said beryllium fluoride in said solvent. (AEC)

Thirty years of fluoridation: a review.

PubMed

Richmond, V L

1985-01-01

Fluoride contributes to stability of both teeth and bones and to reduction of caries, especially if ingested before eruption of teeth. Reduction of caries continues at about 60% in persons drinking fluoridated water only as long as fluoride washes over teeth. One-half the population of the US does not have access to water with an optimal fluoride concentration of about 1 mg/L. Misinformation about fluoridation contributes to reluctance of communities to supplement the natural but inadequate fluoride of those water supplies. Fluoridation of water has no positive or negative effect on incidence or mortality rates due to cancer, heart disease, intracranial lesions, nephritis, cirrhosis, mongoloid births, or from all causes together. The collective decision to increase the natural fluoride content of water supplies is not an infringement of civil rights, nor does it establish a precedent in the binding sense of the law. Supplemental fluoride in water makes it available to all members of the community in a safe, practical, economical and reliable manner. Fluoridation saves money in dental costs and time lost from work. Fluoridation is an appropriate action of government in promoting the health and welfare of society.

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

Rothman, A.; Graczyk, D.; Chemical Sciences and Engineering Division

In the ammonium diuranate (ADU) process, UF{sub 6} is reacted with water, and the acidic solution of uranyl fluoride is treated with aqueous ammonia to precipitate ammonium polyuranate for subsequent reduction to UO{sub 2} and production of fuel pellets for commercial nuclear reactors. Our experiments simulated adding aqueous ammonia to the reaction products of UF{sub 6} and water in typical ADU processes. Chemical and X-ray diffraction analysis of products from the experiments are consistent with postulated chemical equilibria in which solids with structures close to that of ammonium polyuranate are formed from co-precipitation of the NH{sub 4}{sup +}(aq) cation withmore » (previously unreported) anions of the form UO{sub 2}F{sub 3-x}(OH){sub x}{sup -}(aq). More efficient separations of solid products were obtained at NH{sub 4}OH:UF{sub 6} ratios of 19 or greater, with x closer to the value of 3 for the hypothetical formation of pure ammonium polyuranate. Supplementary experiments in the current study and a previous study in our laboratory indicated that nominal uranium concentrations of 90 mg/l in the filtrate resulting from such separations could be reduced to microgram per liter levels by batch mixing a 1-to-2.5 aqueous diluate of the filtrate with the Diphonix{reg_sign} ion exchange resin. Our study further demonstrated that reaction of the purified NH{sub 4}OH-NH{sub 4}F diluate with aqueous Ca(OH){sub 2} at 80 to 90 C could produce essentially uranium-free CaF{sub 2} and an ammonia distillate, as useful waste-conversion end products from a modified ADU process.« less

Fluoride in groundwater: toxicological exposure and remedies.

PubMed

Jha, S K; Singh, R K; Damodaran, T; Mishra, V K; Sharma, D K; Rai, Deepak

2013-01-01

Fluoride is a chemical element that is found most frequently in groundwater and has become one of the most important toxicological environmental hazards globally. The occurrence of fluoride in groundwater is due to weathering and leaching of fluoride-bearing minerals from rocks and sediments. Fluoride when ingested in small quantities (<0.5 mg/L) is beneficial in promoting dental health by reducing dental caries, whereas higher concentrations (>1.5 mg/L) may cause fluorosis. It is estimated that about 200 million people, from among 25 nations the world over, may suffer from fluorosis and the causes have been ascribed to fluoride contamination in groundwater including India. High fluoride occurrence in groundwaters is expected from sodium bicarbonate-type water, which is calcium deficient. The alkalinity of water also helps in mobilizing fluoride from fluorite (CaF2). Fluoride exposure in humans is related to (1) fluoride concentration in drinking water, (2) duration of consumption, and (3) climate of the area. In hotter climates where water consumption is greater, exposure doses of fluoride need to be modified based on mean fluoride intake. Various cost-effective and simple procedures for water defluoridation techniques are already known, but the benefits of such techniques have not reached the rural affected population due to limitations. Therefore, there is a need to develop workable strategies to provide fluoride-safe drinking water to rural communities. The study investigated the geochemistry and occurrence of fluoride and its contamination in groundwater, human exposure, various adverse health effects, and possible remedial measures from fluoride toxicity effects.

Rational Ligand Design for U(VI) and Pu(IV)

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

Szigethy, Geza

2009-08-12

Nuclear power is an attractive alternative to hydrocarbon-based energy production at a time when moving away from carbon-producing processes is widely accepted as a significant developmental need. Hence, the radioactive actinide power sources for this industry are necessarily becoming more widespread, which is accompanied by the increased risk of exposure to both biological and environmental systems. This, in turn, requires the development of technology designed to remove such radioactive threats efficiently and selectively from contaminated material, whether that be contained nuclear waste streams or the human body. Raymond and coworkers (University of California, Berkeley) have for decades investigated the interactionmore » of biologically-inspired, hard Lewis-base ligands with high-valent, early-actinide cations. It has been established that such ligands bind strongly to the hard Lewis-acidic early actinides, and many poly-bidentate ligands have been developed and shown to be effective chelators of actinide contaminants in vivo. Work reported herein explores the effect of ligand geometry on the linear U(IV) dioxo dication (uranyl, UO 2 2+). The goal is to utilize rational ligand design to develop ligands that exhibit shape selectivity towards linear dioxo cations and provides thermodynamically favorable binding interactions. The uranyl complexes with a series of tetradentate 3-hydroxy-pyridin-2-one (3,2-HOPO) ligands were studied in both the crystalline state as well as in solution. Despite significant geometric differences, the uranyl affinities of these ligands vary only slightly but are better than DTPA, the only FDA-approved chelation therapy for actinide contamination. The terepthalamide (TAM) moiety was combined into tris-beidentate ligands with 1,2- and 3,2-HOPO moieties were combined into hexadentate ligands whose structural preferences and solution thermodynamics were measured with the uranyl cation. In addition to achieving coordinative saturation, these ligands exhibited increased uranyl affinity compared to bis-Me-3,2-HOPO ligands. This result is due in part to their increased denticity, but is primarily the result of the presence of the TAM moiety. In an effort to explore the relatively unexplored coordination chemistry of Pu(IV) with bidentate moieties, a series of Pu(IV) complexes were also crystallized using bidentate hydroxypyridinone and hydroxypyrone ligands. The geometries of these complexes are compared to that of the analogous Ce(IV) complexes. While in some cases these showed the expected structural similarities, some ligand systems led to significant coordination changes. A series of crystal structure analyses with Ce(IV) indicated that these differences are most likely the result of crystallization condition differences and solvent inclusion effects.« less

Chronologic Trends in Studies on Fluoride Mechanisms of Action.

PubMed

Oh, H J; Oh, H W; Lee, D W; Kim, C H; Ahn, J Y; Kim, Y; Shin, H B; Kim, C Y; Park, S H; Jeon, J G

2017-11-01

Fluoride has been widely used for the prevention of dental caries since the mid-20th century. The aim of this study was to investigate the chronologic trends in studies on fluoride mechanisms of action against dental caries during the years 1950 to 2015. To this aim, queries such as "fluoride," "fluoride and demineralization," "fluoride and remineralization," "fluoride and (plaque or biofilms)," and "fluoride and (bacteria or microbials)" were submitted to PubMed to collect research article information, including titles, abstracts, publication dates, author affiliations, and publication journals. The article information that PubMed produced was then collected by an automatic web crawler and examined through informetrics and linguistic analyses. We found that the number of articles concerned with fluoride mechanisms of action against dental caries was 6,903 and gradually increased over time during the years 1950 to 2015. They were published by 1,136 journals-most notably, Caries Research and Journal of Dental Research. Of the articles published, those related to bacteria/microbials had a higher percentage (44%) than those dealing with plaque/biofilms, demineralization, and remineralization. With regard to the geographic distribution of authors, Europe and North America accounted for 65% of the articles during the years 1987 to 2015, although the number of authors in Asia sharply increased in recent years. Among the fluoride compounds, NaF was mentioned more frequently than SnF 2 , Na 2 PO 3 F, amine fluoride, and acidulated phosphate fluoride during the years 1986 to 2015. Water fluoridation received the most attention among the various fluoride application methods (toothpastes, mouthwashes, fluoride varnishes, and fluoride gels) during the same period. These results, obtained from employing informetrics and linguistic analyses, suggest that in studies on fluoride mechanisms of action, 1) the unbalanced geographic distribution of articles and 2) the heavy concentration of articles on particular fluoride compounds and application methods should be overcome in future research.

Fluoride content of infant formulas prepared with deionized, bottled mineral and fluoridated drinking water.

PubMed

Buzalaf, M A; Granjeiro, J M; Damante, C A; de Ornelas, F

2001-01-01

Usually infant milk formula is the major source of fluoride in infancy. Fluoride concentrations in ten samples of powdered milk formulas, prepared with deionized, bottled mineral, and fluoridated drinking water were determined after HMDS-facilitated diffusion, using a fluoride ion specific electrode(Orion 9609). Fluoride concentrations ranged from 0.01 to 0.75 ppm; from 0.02 to 1.37 ppm and from 0.91 to 1.65 ppm for formulas prepared with deionized, bottled mineral (0.02 to 0.69 ppm F) and fluorinated drinking water (0.9 ppm F), respectively. Possible fluoride ingestion per Kg body mass ws estimated. With deionized water, only the soy-based- formulas should provide a daily fluoride intake of above the suggested threshold for fluorosis. With water containing 0.9 ppm F, however, all of them would provide it. Hence, to limit fluoride intakes to amounts <0.1 mg/kg/day, it is necessary to avoid use fo fluoridated water (around 1 ppm) to dilute powdered infant formulas.

The fractional urinary fluoride excretion of adults consuming naturally and artificially fluoridated water and the influence of water hardness: a randomized trial.

PubMed

Villa, A; Cabezas, L; Anabalón, M; Rugg-Gunn, A

2009-09-01

To assess whether there was any significant difference in the average fractional urinary fluoride excretion (FUFE) values among adults consuming (NaF) fluoridated Ca-free water (reference water), naturally fluoridated hard water and an artificially (H2SiF6) fluoridated soft water. Sixty adult females (N=20 for each treatment) participated in this randomized, double-blind trial. The experimental design of this study provided an indirect estimation of the fluoride absorption in different types of water through the assessment of the fractional urinary fluoride excretion of volunteers. Average daily FUFE values (daily amount of fluoride excreted in urine/daily total fluoride intake) were not significantly different between the three treatments (Kruskal-Wallis; p = 0.62). The average 24-hour FUFE value (n=60) was 0.69; 95% C.I. 0.65-0.73. The results of this study suggest that the absorption of fluoride is not affected by water hardness.

Does fluoride in the water close the dental caries gap between Indigenous and non-Indigenous children?

PubMed

Lalloo, R; Jamieson, L M; Ha, D; Ellershaw, A; Luzzi, L

2015-09-01

Indigenous children experience significantly more dental caries than non-Indigenous children. This study assessed if access to fluoride in the water closed the gap in dental caries between Indigenous and non-Indigenous children. Data from four states and two territories were sourced from the Child Dental Health Survey (CDHS) conducted in 2010. The outcomes were dental caries in the deciduous and permanent dentitions, and the explanatory variables were Indigenous status and access to fluoridated water (≥0.5 mg/L) prior to 2008. Dental caries prevalence and severity for Indigenous and non-Indigenous children, in both dentitions, was lower in fluoridated areas compared to non-fluoridated areas. Among non-Indigenous children, there was a 50.9% difference in mean dmft scores in fluoridated (1.70) compared to non-fluoridated (2.86) areas. The difference between Indigenous children in fluoridated (3.29) compared to non-fluoridated (4.16) areas was 23.4%. Among non-Indigenous children there was a 79.7% difference in the mean DMFT scores in fluoridated (0.68) compared to non-fluoridated (1.58) areas. The difference between Indigenous children in fluoridated (1.59) and non-fluoridated (2.23) areas was 33.5%. Water fluoridation is effective in reducing dental caries, but does not appear to close the gap between non-Indigenous children and Indigenous children. © 2015 Australian Dental Association.

Fluoride bioavailability in saliva and plaque

PubMed Central

2012-01-01

Background Different fluoride formulations may have different effects on caries prevention. It was the aim of this clinical study to assess the fluoride content, provided by NaF compared to amine fluoride, in saliva and plaque. Methods Eight trained volunteers brushed their teeth in the morning for 3 minutes with either NaF or amine fluoride, and saliva and 3-day-plaque-regrowth was collected at 5 time intervals during 6 hours after tooth brushing. The amount of collected saliva and plaque was measured, and the fluoride content was analysed using a fluoride sensitive electrode. All subjects repeated all study cycles 5 times, and 3 cycles per subject underwent statistical analysis using the Wilcoxon-Mann-Whitney test. Results Immediately after brushing the fluoride concentration in saliva increased rapidly and dropped to the baseline level after 360 minutes. No difference was found between NaF and amine fluoride. All plaque fluoride levels were elevated after 30 minutes until 120 minutes after tooth brushing, and decreasing after 360 minutes to baseline. According to the highly individual profile of fluoride in saliva and plaque, both levels of bioavailability correlated for the first 30 minutes, and the fluoride content of saliva and plaque was back to baseline after 6 hours. Conclusions Fluoride levels in saliva and plaque are interindividually highly variable. However, no significant difference in bioavailability between NaF and amine fluoride, in saliva, or in plaque was found. PMID:22230722

Gramicidin D enhances the antibacterial activity of fluoride.

PubMed

Nelson, James W; Zhou, Zhiyuan; Breaker, Ronald R

2014-07-01

Fluoride is a toxic anion found in many natural environments. One of the major bacterial defenses against fluoride is the cell envelope, which limits passage of the membrane-impermeant fluoride anion. Accordingly, compounds that enhance the permeability of bacterial membranes to fluoride should also enhance fluoride toxicity. In this study, we demonstrate that the pore-forming antibiotic gramicidin D increases fluoride uptake in Bacillus subtilis and that the antibacterial activity of this compound is potentiated by fluoride. Polymyxin B, another membrane-targeting antibiotic with a different mechanism of action, shows no such improvement. These results, along with previous findings, indicate that certain compounds that destabilize bacterial cell envelopes can enhance the toxicity of fluoride. Copyright © 2014 Elsevier Ltd. All rights reserved.

The effect on human salivary fluoride concentration of consuming fluoridated salt-containing baked food items.

PubMed

Macpherson, L M; Stephen, K W

2001-10-01

Salt fluoridation is recognised world-wide as a proven and viable alternative means of consumer choice-related, community-based fluoridation where water fluoridation is either technically or politically impossible. However, as most salt consumed is contained within cooked food products, rather than sprinkled over prepared food at the table, the purpose of this study was to investigate the effects on salivary fluoride concentration of consuming baked food products prepared with 250 and 350 ppm fluoridated salt (as KF). Six food items were baked with (a) normal non-fluoridated salt, (b) 250 mg F/kg salt and (c) 350 mg F/kg salt. Eleven adult volunteers consumed these foodstuffs on separate occasions and salivary samples were collected for fluoride analyses before and at various time points (1-30 min) after eating. For most foodstuffs, small but significant increases in salivary fluoride concentration occurred for at least 5 min after ingestion of the fluoridated salt-containing items. Salivary fluoride concentrations peaked 1 or 2 min after eating, with highest values for the six test foods ranging from 0.16 to 0.25 ppm F, and from 0.18 to 0.44 ppm F for the 250 and 350 mg F/kg salt products, respectively. In all cases, salivary fluoride concentrations had returned to baseline by 20 min. The clinical significance of such small, short-term increases in salivary fluoride is uncertain, but the findings suggest that a more frequent intake of foods with fluoridated salt substituted for normal salt could help sustain slightly elevated salivary fluoride concentrations for more prolonged periods of the day, and might thus potentiate the cariostatic effects of saliva on tooth mineral.

Comparing activated alumina with indigenous laterite and bauxite as potential sorbents for removing fluoride from drinking water in Ghana

USGS Publications Warehouse

Craig, Laura; Stillings, Lisa; Decker, David L.; Thomas, James M.

2015-01-01

Fluoride is considered beneficial to teeth and bones when consumed in low concentrations, but at elevated concentrations it can cause dental and skeletal fluorosis. Most fluoride-related health problems occur in poor, rural communities of the developing world where groundwater fluoride concentrations are high and the primary sources of drinking water are from community hand-pump borehole drilled wells. One solution to drinking high fluoride water is to attach a simple de-fluoridation filter to the hand-pump; and indigenous materials have been recommended as low-cost sorbents for use in these filters. In an effort to develop an effective, inexpensive, and low-maintenance de-fluoridation filter for a high fluoride region in rural northern Ghana, this study conducted batch fluoride adsorption experiments and potentiometric titrations to investigate the effectiveness of indigenous laterite and bauxite as sorbents for fluoride removal. It also determined the physical and chemical properties of each sorbent. Their properties and the experimental results, including fluoride adsorption capacity, were then compared to those of activated alumina, which has been identified as a good sorbent for removing fluoride from drinking water. The results indicate that, of the three sorbents, bauxite has the highest fluoride adsorption capacity per unit area, but is limited by a low specific surface area. When considering fluoride adsorption per unit weight, activated alumina has the highest fluoride adsorption capacity because of its high specific surface area. Activated alumina also adsorbs fluoride well in a wider pH range than bauxite, and particularly laterite. The differences in adsorption capacity are largely due to surface area, pore size, and mineralogy of the sorbent.

Concentration of Fluoride in Cow's and Buffalo's Milk in Relation to Varying Levels of Fluoride Concentration in Drinking Water of Mathura City in India- A Pilot Study.

PubMed

Gupta, Prahlad; Gupta, Nidhi; Meena, Komal; Moon, Ninad Joshirao; Kumar, Puneet; Kaur, Ravneet

2015-05-01

To estimate fluoride concentration in drinking water, cow's milk and buffalo's milk and to correlate the concentration of fluoride in cow's milk and buffalo's milk with varying levels of fluoride concentration in drinking water. Ten households having both cows and buffalo's were selected by convenience in each of the 3 zones (below optimum fluoride <0.7 ppm (parts per million), optimum fluoride 0.7-1.2 ppm and above optimum fluoride areas > 1.2 ppm). From these selected households, 200 ml of fresh milk of both cows and buffaloes was collected along with 200 ml of drinking water for estimation of fluoride concentration by using a fluoride ion selective electrode method. The data was analysed using SPSS, version 11.5 for windows. The mean fluoride concentration of drinking water, cow's milk and buffalo's milk in three different fluoride zones was 0.89±0.39, 0.09±0.07, 0.09±0.08 respectively. Pearson's correlation found a statistically significant correlation between fluoride concentrations in cow's and buffalo's milk with varying levels of fluoride concentration in drinking water in zone B and zone C. However, this correlation was not statistically significant in zone A. With an increase in fluoride concentration in drinking water there was an increase in concentration of fluoride in cow's and buffalo's milk. We conclude that this association is seen in conjunction to not only a single factor but rather due to culmination of several other aspects. So, there is a need to elucidate the other factors that might be contributing to this increase and dental fluorosis.

Level of Fluoride in Soil, Grain and Water in Jalgaon District, Maharashtra, India.

PubMed

Naik, Rahul Gaybarao; Dodamani, Arun Suresh; Vishwakarma, Prashanth; Jadhav, Harish Chaitram; Khairnar, Mahesh Ravindra; Deshmukh, Manjiri Abhay; Wadgave, Umesh

2017-02-01

Fluoride has an influence on both oral as well as systemic health. The major source of fluoride to body is through drinking water as well as through diet. Staple diet mainly depends on local environmental factors, food grains grown locally, its availability etc. Determination of fluoride level in these food grains is important. So, estimation of the amount of fluoride in grains and its relation to the sources of fluoride used for their cultivation viz., soil and water is important. To estimate the relation of fluoride concentration in grains (Jowar) with respect to that of soil and water used for their cultivation. Fifteen samples each of soil, water and grains were collected using standardized method from the same farm fields of randomly selected villages of Jalgaon district. Fluoride ion concentration was determined in laboratory using SPADNS technique. Mean difference in fluoride levels in between the groups were analyzed using ANOVA and Post-Hoc Tukey test. Linear regression method was applied to analyse the association of the fluoride content of grain with water and soil. There was a significant difference in between mean fluoride levels of soil and water (p<0.001) and in between soil and grain (p<0.001); however, difference in between mean fluoride levels of water and grain was found to be non significant (p=0.591). Also fluoride levels in all the three groups showed significant association with each other. Fluoride level of soil, grains and water should be adjusted to an optimum level. Soil has positive correlation with respect to uptake of fluoride by Jowar grains. So, Jowar grains with optimum fluoride content should be made available in the commercial markets so that oral and general health can be benefitted.

Development of resistance of mutans streptococci and Porphyromonas gingivalis to chlorhexidine digluconate and amine fluoride/stannous fluoride-containing mouthrinses, in vitro.

PubMed

Kulik, Eva M; Waltimo, Tuomas; Weiger, Roland; Schweizer, Irene; Lenkeit, Krystyna; Filipuzzi-Jenny, Elisabeth; Walter, Clemens

2015-07-01

The aim if this study was to determine the minimal inhibitory concentrations of chlorhexidine digluconate and an amine fluoride/stannous fluoride-containing mouthrinse against Porphyromonas gingivalis and mutans streptococci during an experimental long-term subinhibitory exposition. Five P. gingivalis strains and four mutans streptococci were subcultivated for 20-30 passages in subinhibitory concentrations of chlorhexidine digluconate or an amine fluoride/stannous fluoride-containing mouthrinse. Pre-passaging minimal inhibitory concentrations for chlorhexidine ranged from 0.5 to 2 mg/l for mutans streptococci and from 2 to 4 mg/l for the P. gingivalis isolates. For the amine fluoride/stannous fluoride-containing mouthrinse minimal inhibitory values from 0.125 to 0.25% for the mutans streptococci and from 0.063 to 0.125% for the P. gingivalis isolates were determined. Two- to fourfold increased minimal inhibitory concentrations against chlorhexidine were detected for two of the five P. gingivalis isolates, whereas no increase in minimal inhibitory concentrations was found for the mutans streptococci after repeated passaging through subinhibitory concentrations. Repeated exposure to subinhibitory concentrations of the amine fluoride/stannous fluoride-containing mouthrinse did not alter the minimally inhibitory concentrations of the bacterial isolates tested. Chlorhexidine and the amine fluoride/stannous fluoride-containing mouthrinse are effective inhibitory agents against the oral bacterial isolates tested. No general development of resistance against chlorhexidine or the amine fluoride/stannous fluoride-containing mouthrinse was detected. However, some strains showed potential to develop resistance against chlorhexidine after prolonged exposure. The use of chlorhexidine should be limited to short periods of time. The amine fluoride/stannous fluoride-containing mouthrinse appears to have the potential to be used on a long-term basis.

An in situ caries study on the interplay between fluoride dose and concentration in milk.

PubMed

Lippert, F; Martinez-Mier, E A; Zero, D T

2014-07-01

This randomized, cross-over in situ study investigated the impact of sodium fluoride dose and concentration in milk on caries lesion rehardening, fluoridation and acid resistance. Twenty-eight subjects wore two gauze-covered enamel specimens with preformed lesions placed buccally on their mandibular partial dentures for three weeks. Participants used fluoride-free dentifrice throughout the study and consumed once daily one of the five study treatments: no fluoride in 200 ml milk (0F-200), 1.5 or 3 mg fluoride in either 100 (1.5F-100; 3F-100) or 200 ml milk (1.5F-200; 3F-200). After three weeks, specimens were retrieved. Knoop hardness was used to determine rehardening and resistance to a secondary acid challenge. Enamel fluoride uptake (EFU) was determined using a microbiopsy technique. A linear fluoride dose-response was observed for all study variables which exhibited similar overall patterns. All the treatments resulted in rehardening, with 0F-200 inducing the least and 3F-100 the most. Apart from 1.5F-200, all the treatments resulted in statistically significantly more rehardening compared to 0F-200. The fluoride doses delivered in 100 ml provided directionally although not statistically significantly more rehardening than those delivered in 200 ml milk. EFU data exhibited better differentiation between treatments: all fluoridated milk treatments delivered more fluoride to lesions than 0F-200; fluoride in 100 ml demonstrated statistically significantly higher EFU than fluoride in 200 ml milk. Findings for acid resistance were also more discerning than rehardening data. The present study has provided further evidence for the anti-caries benefits of fluoridated milk. Both fluoride dose and concentration appear to impact the cariostatic properties of fluoride in milk. Copyright © 2014 Elsevier Ltd. All rights reserved.

Comparison of short-term in vitro fluoride release and recharge from four different types of pit-and-fissure sealants.

PubMed

Koga, Hiroshi; Kameyama, Atsushi; Matsukubo, Takashi; Hirai, Yoshito; Takaesu, Yoshinori

2004-08-01

The purpose of this in vitro study was to assess the effects of four commercial fluoride-containing pit-and-fissure sealants on caries prevention. Four sealants containing fluoride, Fuji III, Fuji III LC (GC Co., Tokyo), Teethmate F-1 (Kuraray Medical Co., Osaka) and Helioseal F (Vivadent Co., Liechtenstein) were used to investigate fluoride release and recharge. Disk-shaped specimens prepared from each material were immersed in distilled water at a temperature of 37 degrees C. After seven days, acidulated phosphate fluoride solution (APF) was applied to each specimen, and it was then again immersed in distilled water for 14 days. We then determined how much fluoride had been released into the immersing water. Fuji III LC was used with APF solution to investigate the fluoride uptake. Fuji III had the highest fluoride release, and Fuji III LC had the highest fluoride recharge. Helioseal F and Teethmate F-1 had almost no fluoride recharge. Fuji III LC/APF had a higher fluoride uptake to enamel than Fuji III LC. These results suggest that GIC-sealants in the oral cavity can serve as a fluoride reservoir and contribute to retaining a low fluoride level in oral fluids, thereby preventing caries.

Low-levels of fluoride in plaque and saliva and their effects on the demineralisation and remineralisation of enamel; role of fluoride toothpastes.

PubMed

Lynch, R J M; Navada, R; Walia, R

2004-01-01

To summarise support for current consensus on the likely means by which fluoride toothpastes reduce caries and review some relevant studies of the effect of low levels of fluoride on the demineralisation and remineralisation of enamel. The major anti-caries effect of fluoride toothpastes is thought to result from small but protracted elevations in levels of fluoride in plaque and saliva. Fluoride incorporated into enamel systemically does not reduce enamel solubility sufficiently to exert an anti-caries effect. Fluoride has the potential to exert an anti-caries benefit largely through three mechanisms; inhibition of demineralisation, promotion of remineralisation and interference with bacterial growth and metabolism. However, the low levels of fluoride thought to influence caries are insufficient to have a significant effect via the latter mechanism. Thus reductions in caries resulting from the use of fluoride toothpastes can be linked to modification of the demineralisation/remineralisation balance by direct effects on dental mineral exerted topically by low levels of fluoride. Numerous in vitro studies have shown that low levels of fluoride, typical of those found after many hours in resting plaque and saliva, and resulting from the regular use of fluoride toothpastes, can have a profound effect on enamel demineralisation and remineralisation.

Groundwater fluoride contamination and its possible health implications in Indi taluk of Vijayapura District (Karnataka State), India.

PubMed

Ugran, Vidyavati; Desai, Naveen N; Chakraborti, Dipankar; Masali, Kallappa A; Mantur, Prakash; Kulkarni, Shreepad; Deshmukh, Niranjan; Chadchan, Kailash S; Das, Swastika N; Tanksali, Anuradha S; Arwikar, Asha S; Guggarigoudar, Suresh P; Vallabha, Tejaswini; Patil, Shailaja S; Das, Kusal K

2017-10-01

Groundwater fluoride concentration and fluoride-related health problems were studied in twenty-two villages of Indi taluk of Vijayapura district, Karnataka, India. Present study (2015) was also used to compare groundwater fluoride concentration in same 22 villages with previous government report (2000). Groundwater fluoride concentrations of 62 bore wells of 22 villages were analyzed by using an ion-sensitive electrode. A total of 660 adults and 600 children were screened for fluorosis symptoms and signs. Sixty clinically suspected fluorosis patients' urine samples were further analyzed for fluoride. The mean value (1.22 ± 0.75 mg/L) of fluoride concentration of 62 bore wells and 54.83 % bore wells with ≥1.0 mg/L of fluoride concentrations in Indi taluk indicates higher than the permissible limit of drinking water fluoride concentration recommended for India. Clinical symptoms like arthritis, joint pains, gastrointestinal discomfort and lower limb deformities with high urinary fluoride concentrations in some subjects suggest fluorosis. Results also showed an increase in groundwater fluoride concentration of the same 22 villages between previous and present study. Preliminary arthritis symptom of the villagers could be due to drinking fluoride-contaminated water. Increase in fluoride concentration with time to the bore wells definitely indicates future danger.

Black Tea Source, Production, and Consumption: Assessment of Health Risks of Fluoride Intake in New Zealand

PubMed Central

Godfrey, Michael; Limeback, Hardy

2017-01-01

In countries with fluoridation of public water, it is imperative to determine other dietary sources of fluoride intake to reduce the public health risk of chronic exposure. New Zealand has one of the highest per capita consumption rates of black tea internationally and is one of the few countries to artificially fluoridate public water; yet no information is available to consumers on the fluoride levels in tea products. In this study, we determined the contribution of black tea as a source of dietary fluoride intake by measuring the fluoride content in 18 brands of commercially available products in New Zealand. Fluoride concentrations were measured by potentiometric method with a fluoride ion-selective electrode and the contribution of black tea to Adequate Intake (AI) and Tolerable Upper Intake Level (UL) was calculated for a range of consumption scenarios. We examined factors that influence the fluoride content in manufactured tea and tea infusions, as well as temporal changes in fluoride exposure from black tea. We review the international evidence regarding chronic fluoride intake and its association with chronic pain, arthritic disease, and musculoskeletal disorders and provide insights into possible association between fluoride intake and the high prevalence of these disorders in New Zealand. PMID:28713433

Fluoride release from fluoride varnishes under acidic conditions.

PubMed

Lippert, F

2014-01-01

The aim was to investigate the in vitro fluoride release from fluoride varnishes under acidic conditions. Poly(methyl methacrylate) blocks (Perspex, n=3 per group) were painted with 80 ± 5 mg fluoride varnish (n=10) and placed into artificial saliva for 30 min. Then, blocks were placed into either 1% citric acid (pH 2.27) or 0.3% citric acid (pH 3.75) solutions (n=3 per solution and varnish) for 30 min with the solutions being replaced every 5 min. Saliva and acid solutions were analyzed for fluoride content. Data were analyzed using three-way ANOVA (varnish, solution, time). The three-way interaction was significant (p>0.0001). Fluoride release and release patterns varied considerably between varnishes. Fluoride release in saliva varied by a factor of more than 10 between varnishes. Some varnishes (CavityShield, Nupro, ProFluorid, Vanish) showed higher fluoride release in saliva than during the first 5 min of acid exposure, whereas other varnishes (Acclean, Enamel-Pro, MI Varnish, Vella) showed the opposite behavior. There was little difference between acidic solutions. Fluoride release from fluoride varnishes varies considerably and also depends on the dissolution medium. Bearing in mind the limitations of laboratory research, the consumption of acidic drinks after fluoride varnish application should be avoided to optimize the benefit/risk ratio.

Urinary fluoride as a monitoring tool for assessing successful intervention in the provision of safe drinking water supply in five fluoride-affected villages in Dhar district, Madhya Pradesh, India.

PubMed

Srikanth, R; Gautam, Anil; Jaiswal, Suresh Chandra; Singh, Pavitra

2013-03-01

Endemic fluorosis was detected in 31 villages in the Dhar district of Madhya Pradesh, Central India. Out of the 109 drinking water sources that were analyzed, about 67 % were found to contain high concentration of fluoride above the permissible level of 1.0 mg/l. Dental fluorosis among the primary school children in the age between 8 and 15 served as primary indicator for fluoride intoxication among the children. Urinary fluoride levels among the adults were found to be correlated with drinking water fluoride in 10 villages affected by fluoride. Intervention in the form of alternate safe water supply in five villages showed significant reduction in the urinary fluoride concentration when compared to the control village. Urinary fluoride serves as an excellent marker for assessing the effectiveness of intervention program in the fluoride-affected villages.

Isothermal vapor-liquid equilibria for the systems 1-chloro-1,1-difluoroethane + hydrogen fluoride, 1,1-dichloro-1-fluoroethane + hydrogen fluoride, and chlorodifluoromethane + hydrogen fluoride

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

Kang, Y.W.; Lee, Y.Y.

1997-03-01

Isothermal vapor-liquid equilibria for the three binary systems (1-chloro-1,1-difluoroethane + hydrogen fluoride, 1,1-dichloro-1-fluoroethane + hydrogen fluoride, and chlorodifluoromethane + hydrogen fluoride) have been measured. The experimental data for the binary systems are correlated with the NRTL equation with the vapor-phase association model for the mixtures containing hydrogen fluoride, and the relevant parameters are presented. All of the systems form minimum boiling heterogeneous azeotropes.

Community effectiveness of public water fluoridation in reducing children's dental disease.

PubMed

Armfield, Jason Mathew

2010-01-01

Water fluoridation is one of the most effective public health programs of the past century. However, efforts to extend water fluoridation into currently non-fluoridated areas are often thwarted. Despite considerable evidence regarding the effectiveness of water fluoridation at an individual level, published national community-based studies are rare. This study compared children's decay experience and prevalence between areas with and without water fluoridation in Australia. Oral health data were obtained from clinical examinations of 128, 990 5- to 15-year-old children attending for a regular visit with their respective Australian state or territory School Dental Service in 2002. Water fluoridation status, residence remoteness, and socioeconomic status (SES) were obtained for each child's recorded residential postcode area. Children from every age group had greater caries prevalence and more caries experience in areas with negligible fluoride concentrations in the water (<0.3 parts per million [ppm]) than in optimally fluoridated areas (> or = 0.7 ppm). Controlling for child age, residential location, and SES, deciduous and permanent caries experience was 28.7% and 31.6% higher, respectively, in low-fluoride areas compared with optimally fluoridated areas. The odds ratios for higher caries prevalence in areas with negligible fluoride compared with optimal fluoride were 1.34 (95% confidence interval [CI] 1.29, 1.39) and 1.24 (95% CI 1.21, 1.28) in the deciduous and permanent dentitions, respectively. This study demonstrates the continued community effectiveness of water fluoridation and provides support for the extension of this important oral health intervention to populations currently without access to fluoridated water.

Fluoride-releasing restorative materials and secondary caries.

PubMed

Hicks, John; Garcia-Godoy, Franklin; Donly, Kevin; Flaitz, Catherine

2003-03-01

Secondary caries is responsible for 60 percent of all replacement restorations in the typical dental practice. Risk factors for secondary caries are similar to those for primary caries development. Unfortunately, it is not possible to accurately predict which patients are at risk for restoration failure. During the past several decades, fluoride-releasing dental materials have become a part of the dentist's armamentarium. Considerable fluoride is released during the setting reaction and for periods up to eight years following restoration placement. This released fluoride is readily taken up by the cavosurface tooth structure, as well as the enamel and root surfaces adjacent to the restoration. Resistance against caries along the cavosurface and the adjacent smooth surface has been shown in both in vitro and in vivo studies. Fluoride-releasing dental materials provide for improved resistance against primary and secondary caries in coronal and root surfaces. Plaque and salivary fluoride levels are elevated to a level that facilitates remineralization. In addition, the fluoride released to dental plaque adversely affects the growth of lactobacilli and mutans streptococci by interference with bacterial enzyme systems. Fluoride recharging of these dental materials is readily achieved with fluoridated toothpastes, fluoride mouthrinses, and other sources of topical fluoride. This allows fluoride-releasing dental materials to act as intraoral fluoride reservoirs. The improvement in the properties of dental materials with the ability to release fluoride has improved dramatically in the past decade, and it is anticipated that in the near future the vast majority of restorative procedures will employ fluoride-releasing dental materials as bonding agents, cavity liners, luting agents, adhesives for orthodontic brackets, and definitive restoratives.

Prevalence of fluorosis and identification of fluoride endemic areas in Manur block of Tirunelveli District, Tamil Nadu, South India

NASA Astrophysics Data System (ADS)

Gopalakrishnan, Subarayan Bothi; Viswanathan, Gopalan; Siva Ilango, S.

2012-12-01

Prevalence of fluorosis is mainly due to the consumption of more fluoride through drinking water. It is necessary to identify the fluoride endemic areas to adopt remedial measures for the people under the risk of fluorosis. The objectives of this study were to identify the exact location of fluoride endemic areas in Manur block of Tirunelveli District and to estimate fluoride exposure level through drinking water for different age groups. Identification of fluoride endemic areas was performed through Isopleth and Google earth mapping techniques. Fluoride level in drinking water samples was estimated by fluoride ion selective electrode method. A systematic clinical survey conducted in 19 villages of Manur block revealed the rate of prevalence of fluorosis. From this study, it has been found that Alavanthankulam, Melapilliyarkulam, Keezhapilliyarkulam, Nadupilliyarkulam, Keezhathenkalam and Papankulam are the fluoride endemic villages, where the fluoride level in drinking water is above 1 mg/l. Consumption of maximum fluoride exposure levels of 0.30 mg/kg/day for infants, 0.27 mg/kg/day for children and 0.15 mg/kg/day for adults were found among the respective age group people residing in high fluoride endemic area. As compared with adequate intake level of fluoride of 0.01 mg/kg/day for infants and 0.05 mg/kg/day for other age groups, the health risk due to excess fluoride intake to the people of Alavanthankulam and nearby areas has become evident. Hence the people of these areas are advised to consume drinking water with optimal fluoride to avoid further fluorosis risks.

In Vitro Inhibition of Enamel Demineralisation by Fluoride-releasing Restorative Materials and Dental Adhesives.

PubMed

Dionysopoulos, Dimitrios; Koliniotou-Koumpia, Eugenia; Helvatzoglou-Antoniades, Maria; Kotsanos, Nikolaos

2016-01-01

To determine the ability of 5 contemporary fluoride-releasing restoratives and 3 fluoride-releasing adhesives to inhibit enamel demineralisation surrounding restorations, and the associations between inhibition and the levels of fluoride released from these materials. Five fluoride-releasing restoratives (Fuji IX GP, Ketac N100, Dyract Extra, Beautifil II and Wave) and 3 fluoride-releasing adhesives (Stae, Prime & Bond NT and Fluoro Bond II) were investigated. Eight disks of each material were prepared. Fluoride release was measured daily using a fluoride-ion-selective electrode for 15 days. Twenty-four cavities for each group were restored with a restorative and an adhesive. Specimens were subjected to thermal stress and stored for 30 days in saline solution. After a 15-day pH-cycling regimen, two 150-μm-thick sections were derived from each specimen. Enamel lesion depth was measured at 0, 100, and 200 μm from each restoration's margin via polarised light microscopy. Of the restoratives investigated, Fuji IX GP released the most fluoride. The fluoride-releasing restoratives tested exhibited shallower enamel lesions than did the control group at all distances tested (p < 0.05). Fuji IX GP yielded significantly lower enamel lesion depth than did the other experimental materials. The depths of enamel lesions did not differ significantly when comparing restoratives applied with a fluoride-releasing adhesive with those applied with a non-fluoride-releasing adhesive. The fluoride-releasing materials tested reduced enamel demineralisation but to different extents, depending on their levels of fluoride release. Fluoride-releasing adhesives did not influence enamel lesion formation.

Alimentary fluoride intake in preschool children

PubMed Central

2011-01-01

Background The knowledge of background alimentary fluoride intake in preschool children is of utmost importance for introducing optimal and safe caries preventive measures for both individuals and communities. The aim of this study was to assess the daily fluoride intake analyzing duplicate samples of food and beverages. An attempt was made to calculate the daily intake of fluoride from food and swallowed toothpaste. Methods Daily alimentary fluoride intake was measured in a group of 36 children with an average age of 4.75 years and an average weight of 20.69 kg at baseline, by means of a double plate method. This was repeated after six months. Parents recorded their child's diet over 24 hours and collected duplicated portions of food and beverages received by children during this period. Pooled samples of food and beverages were weighed and solid food samples were homogenized. Fluoride was quantitatively extracted from solid food samples by a microdiffusion method using hexadecyldisiloxane and perchloric acid. The content of fluoride extracted from solid food samples, as well as fluoride in beverages, was measured potentiometrically by means of a fluoride ion selective electrode. Results Average daily fluoride intake at baseline was 0.389 (SD 0.054) mg per day. Six months later it was 0.378 (SD 0.084) mg per day which represents 0.020 (SD 0.010) and 0.018 (SD 0.008) mg of fluoride respectively calculated per kg bw/day. When adding the values of unwanted fluoride intake from the toothpaste shown in the literature (0.17-1.21 mg per day) the estimate of the total daily intake of fluoride amounted to 0.554-1.594 mg/day and recalculated to the child's body weight to 0.027-0.077 mg/kg bw/day. Conclusions In the children studied, observed daily fluoride intake reached the threshold for safe fluoride intake. When adding the potential fluoride intake from swallowed toothpaste, alimentary intake reached the optimum range for daily fluoride intake. These results showed that in preschool children, when trying to maximize the benefit of fluoride in caries prevention and to minimize its risk, caution should be exercised when giving advice on the fluoride containing components of child's diet or prescribing fluoride supplements. PMID:21974798

SEPARATION OF URANIUM FROM THORIUM AND PROTACTINIUM

DOEpatents

Musgrave, W.K.R.

1959-06-30

This patent relates to the separation of uranium from thorium and protactinium; such mixtures of elements usually being obtained by neutron irradiation of thorium. The method of separating the constituents has been first to dissolve the mixture of elements in concertrated nitric acid and then to remove the protactinium by absorption on manganese dioxide and the uranium by solvent extraction with ether. Prior to now, comparatively large amounts of thorium were extracted with the uranium. According to the invention this is completely prevented by adding sodium diethyldithiocarbamate to the mixture of soluble nitrate salts. The organic salt has the effect of reacting only with the uranyl nitrate to form the corresponding uranyl salt which can then be selectively extracted from the mixture with amyl acetate.

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

Schoendorff, George E.; De Jong, Wibe A.; Gordon, Mark S.

The formation of uranyl dicationic complexes containing water and nitrile (acetonitrile, propionitrile, and benzonitrile) ligands, [UO2(H2O)n(RCN)m]2+, has been studied using density functional theory (DFT) with a relativistic effective core potential (RECP) to account for scalar relativistic effects on uranium. It is shown that nitrile addition is favored over the addition of water ligands. Decomposition of these complexes to [UO2OH(H2O)n(RCN)m]+ by the loss of either H3O+ or (RCN+H)+ is also examined. It is found that this reaction occurs when the coordination sphere of uranyl is unsaturated. Additionally, this reaction is influenced by the size of the nitrile ligand with reactions involvingmore » acetonitrile being the most prevalent.« less

Performance of a hydrogen uranyl phosphate-carbon double-layer solid capacitor

NASA Astrophysics Data System (ADS)

Pham-Thi, M.; Adet, Ph.; Velasco, G.; Colomban, Ph.

1986-05-01

A mixture of commercially available carbon black (C) powders and hydrogen uranyl phosphate (HUP) precipitate can be used as the electrode material for miniaturized double-layer capacitors. A solid cell of C-HUP/HUP/C-HUP has a capacitance of 1 F which, given the device area and thickness of 0.8 sq cm and 0.2 cm respectively, corresponds to an energy density of more than 5 J/cu cm. The charge x voltage factor is higher than 5 x 10 to the -6th s and the working voltage is over 1.6 V. The leakage current is lower than 3 microamps at room temperature. The electrolyte can be operated up to about 120 C if the device is hermetically sealed.

Laser removal of loose uranium compound contamination from metal surfaces

NASA Astrophysics Data System (ADS)

Roberts, D. E.; Modise, T. S.

2007-04-01

Pulsed laser removal of surface contamination of uranyl nitrate and uranium dioxide from stainless steel has been studied. Most of the loosely bound contamination has been removed at fluence levels below 0.5 J cm -2, leaving about 5% fixed contamination for uranyl nitrate and 15% for uranium dioxide. Both alpha and beta activities are then sufficiently low that contaminated objects can be taken out of a restricted radiation area for re-use. The ratio of beta to alpha activity is found to be a function of particle size and changes during laser removal. In a separate experiment using technetium-99m, the collection of removed radioactivity in the filter was studied and an inventory made of removed and collected contamination.

Effects of oral doses of fluoride on nestling European starlings

USGS Publications Warehouse

Fleming, W.J.; Grue, C.E.; Schuler, C.A.; Bunck, C.M.

1987-01-01

Nestling European starlings (Sturnus vulgaris), raised and fed by free-living adults, were given daily oral doses of either distilled water, 193 mg sodium as Na2CO3 per kg of body weight (sodium control group), or 6, 10, 13, 17,23, 30, 40, 80, 160 mg of the fluoride ion as NaF in distilled water per kg of body weight (mg/kg). Dosing began when nestlings were 24-48 hr old and continued for 16 days. The 24-hr LD50 of fluoride for day-old starlings was 50 mg/kg. The 16-day LD50 was 17 mg/kg. The sodium control group did not differ from the water control group with respect to any of the measured variables. Growth rates were significantly reduced in the 13 and 17 mg of fluoride/kg groups; weights of birds given higher dose levels were omitted from growth comparisons because of high, fluoride-induced mortality. Although pre-fledging weights for the 10, 13, and 17 mg of fluoride/kg groups averaged 3.6 to 8.6% less than controls at 17 days, this difference was not significant. Feather and bone growth of the fluoride and control groups were not different, except for keel length measured at 17 days of age which averaged less in the fluoride groups. Liver and spleen weights were not affected by fluoride treatments. No histological damage related to fluoride treatments was found in liver, spleen, or kidney. The logarithm of bone fluoride and magnesium concentration increased with the logarithm of increasing fluoride treatment levels and were significantly correlated with each other. Fluoride treatments had no effect on percent calcium or phosphorus in bone or plasma alkaline phosphatase activity. Oral doses of fluoride appear to be more toxic than equivalent dietary levels. Most birds probably acquire fluoride through their diet. Therefore, the results of the study may overestimate the potential effects of fluorides on songbirds living in fluoride-contaminated environments.

PTH (1-34) affects bone turnover governed by osteocytes exposed to fluoride.

PubMed

Yu, Xiuhua; Yu, Haolan; Jiang, Ningning; Zhang, Xiuyun; Zhang, Mengmeng; Xu, Hui

2018-05-15

Exposure to fluoride from environmental sources remains an overlooked, but serious public health risk. In this study, we looked into the role osteocytes play on the mechanism underlying fluoride induced osteopathology. We analyzed bone formation and resorption related genes generated by osteocytes that were exposed to varied doses of fluoride with and without PTH in vitro. Correspondingly, osteogenesis and osteoclastogenesis related genes were also investigated in rats exposed to fluoride for 8 weeks, and the PTH(1-34)was applied at the last 3 weeks to observe its role in regulating bone turnover upon fluoride treatment. The data in vitro indicated that fluoride treatment inhibited Sost expression of mRNA and protein and stimulated RANKL mRNA protein expression as well as the RANKL/OPG ratio in the primary osteocytes. Single PTH treatment played the similar role on expression of these genes and proteins. The PTH combined administration enhanced the action of fluoride treatment on RNAKL/OPG and SOST/Sclerostin. The up-regulation of RANKL and decreasing of Sost induced by fluoride and/or PTH treatment was validated in vivo and suggests that osteocytes are a major source of RANKL and Sost, both of which play essential roles in fluoride affecting osteogenesis and osteoclastogenesis. Expression of Wnt/β-catenin was up-regulated in both in vitro osteocytes treated with high dose of fluoride and bone tissue of rats in the presence of fluoride and PTH. In vivo, fluoride and single PTH stimulated bone turnover respectively, furthermore, PTH combined with low dose of fluoride treatment reinforced the osteogenesis and osteoclastogenesis genes expression, however, co-treatment of PTH reversed the effect of high dose of fluoride on osteogenesis and osteoclastogenensis related factors. In conclusion, this study demonstrated that osteocytes play a key role in fluoride activated bone turnover, and PTH participates in the process of fluoride modulating SOST/Sclerostin and RANKL expression. Copyright © 2018 Elsevier B.V. All rights reserved.

Effect of exercise on fluoride metabolism in adult humans: a pilot study.

PubMed

V Zohoori, Fatemeh; Innerd, Alison; Azevedo, Liane B; Whitford, Gary M; Maguire, Anne

2015-11-19

An understanding of all aspects of fluoride metabolism is critical to identify its biological effects and avoid fluoride toxicity in humans. Fluoride metabolism and subsequently its body retention may be affected by physiological responses to acute exercise. This pilot study investigated the effect of exercise on plasma fluoride concentration, urinary fluoride excretion and fluoride renal clearance following no exercise and three exercise intensity conditions in nine healthy adults after taking a 1-mg Fluoride tablet. After no, light, moderate and vigorous exercise, respectively, the mean (SD) baseline-adjusted i) plasma fluoride concentration was 9.6(6.3), 11.4(6.3), 15.6(7.7) and 14.9(10.0) ng/ml; ii) rate of urinary fluoride excretion over 0-8 h was 46(15), 44(22), 34(17) and 36(17) μg/h; and iii) rate of fluoride renal clearance was 26.5(9.0), 27.2(30.4), 13.1(20.4) and 18.3(34.9) ml/min. The observed trend of a rise in plasma fluoride concentration and decline in rate of fluoride renal clearance with increasing exercise intensity needs to be investigated in a larger trial. This study, which provides the first data on the effect of exercise with different intensities on fluoride metabolism in humans, informs sample size planning for any subsequent definitive trial, by providing a robust estimate of the variability of the effect.

Fluoride metabolism.

PubMed

Buzalaf, Marília Afonso Rabelo; Whitford, Gary Milton

2011-01-01

Knowledge of all aspects of fluoride metabolism is essential for comprehending the biological effects of this ion in humans as well as to drive the prevention (and treatment) of fluoride toxicity. Several aspects of fluoride metabolism - including gastric absorption, distribution and renal excretion - are pH-dependent because the coefficient of permeability of lipid bilayer membranes to hydrogen fluoride (HF) is 1 million times higher than that of F(-). This means that fluoride readily crosses cell membranes as HF, in response to a pH gradient between adjacent body fluid compartments. After ingestion, plasma fluoride levels increase rapidly due to the rapid absorption from the stomach, an event that is pH-dependent and distinguishes fluoride from other halogens and most other substances. The majority of fluoride not absorbed from the stomach will be absorbed from the small intestine. In this case, absorption is not pH-dependent. Fluoride not absorbed will be excreted in feces. Peak plasma fluoride concentrations are reached within 20-60 min following ingestion. The levels start declining thereafter due to two main reasons: uptake in calcified tissues and excretion in urine. Plasma fluoride levels are not homeostatically regulated and vary according to the levels of intake, deposition in hard tissues and excretion of fluoride. Many factors can modify the metabolism and effects of fluoride in the organism, such as chronic and acute acid-base disturbances, hematocrit, altitude, physical activity, circadian rhythm and hormones, nutritional status, diet, and genetic predisposition. These will be discussed in detail in this review. Copyright © 2011 S. Karger AG, Basel.

[Fluoridation of drinking water, why is it needed?].

PubMed

Zusman, S P; Natapov, L; Ramon, T

2004-01-01

Dental caries is a widespread disease. It causes irreversible damage, pain and considerable expense. Fluoride is the only known substance that raises the tooth's resistance to acid attack. Natural drinking waters contain fluoride at different concentration. The most effective method of fluoride administration to the community level is by adjustng the fluoride concentration in the drinking water to about 1 part per million. To describe the mode of action of fluoride, methods of administration and to describe water fluoridation, advantages and disadvantages. Fluoridation of drinking water started in 1945 in the world and in 1981 in Israel. Today more then 300 million people in some 60 countries enjoy the defending effect of fluoride in drinking water. This is the most effective method for decreasing incidence of caries, as well as being cost effective. Over the years there were many attempts to 'blame' fluoridation with negative side effects to human health. Till today, none of the allegations passed scientific scrutiny. There is overwhelming scientific support for the Regulations that oblige the Water supplier to adjust fluoride levels to 1 ppm in every town or municipality with more then 5,000 inhabitants.

Community water fluoridation on the Internet and social media.

PubMed

Mertz, Aaron; Allukian, Myron

2014-01-01

In the United States, 95 percent of teens and 85 percent of adults use the Internet. Two social media outlets, Facebook and Twitter, reach more than 150 billion users. This study describes anti-fluoridation activity and dominance on the Internet and social media, both of which are community water fluoridation (CWF) information sources. Monthly website traffic to major fluoridation websites was determined from June 2011 to May 2012. Facebook, Twitter, and YouTube fluoridation activity was categorized as "proCWF" or "anti-CWF." Twitter's anti-CWF tweets were further subcategorized by the argument used against CWF. Anti-CWF website traffic was found to exceed proCWF activity five- to sixty-fold. Searching "fluoride" and "fluoridation" on Facebook resulted in 88 to 100 percent anti-CWF groups and pages; "fluoridation" on Twitter and YouTube resulted in 64 percent anti-CWF tweets and 99 percent anti-CWF videos, respectively. "Cancer, " "useless, " and "poisonous" were the three major arguments used against fluoridation. Anti-fluoridation information significantly dominates the Internet and social media. Thousands of people are being misinformed daily about the safety, health, and economic benefits of fluoridation.

The Impact of Fluoride on Ameloblasts and the Mechanisms of Enamel Fluorosis

PubMed Central

Bronckers, A.L.J.J.; Lyaruu, D.M.; DenBesten, P.K.

2009-01-01

Intake of excess amounts of fluoride during tooth development cause enamel fluorosis, a developmental disturbance that makes enamel more porous. In mild fluorosis, there are white opaque striations across the enamel surface, whereas in more severe cases, the porous regions increase in size, with enamel pitting, and secondary discoloration of the enamel surface. The effects of fluoride on enamel formation suggest that fluoride affects the enamel-forming cells, the ameloblasts. Studies investigating the effects of fluoride on ameloblasts and the mechanisms of fluorosis are based on in vitro cultures as well as animal models. The use of these model systems requires a biologically relevant fluoride dose, and must be carefully interpreted in relation to human tooth formation. Based on these studies, we propose that fluoride can directly affect the ameloblasts, particularly at high fluoride levels, while at lower fluoride levels, the ameloblasts may respond to local effects of fluoride on the mineralizing matrix. A new working model is presented, focused on the assumption that fluoride increases the rate of mineral formation, resulting in a greater release of protons into the forming enamel matrix. PMID:19783795

Assessment of fluoride-induced changes on physicochemical and structural properties of bone and the impact of calcium on its control in rabbits.

PubMed

Gopalakrishnan, Subarayan Bothi; Viswanathan, Gopalan

2012-03-01

Bone deformities caused by the chronic intake of large quantities of fluoride and the beneficial effect of calcium on its control have been studied for many years, but only limited data are available on the quantitative effect of fluoride intake and the beneficial impact of calcium on fluoride-induced changes in bone at the molecular level. It is necessary to determine the degree of fluoride-induced changes in bone at different levels of fluoride intake to evaluate the optimum safe intake level of fluoride for maintaining bone health and quality. The ameliorative effect of calcium at different dose levels on minimizing fluoride-induced changes in bone is important to quantify the amount of calcium intake necessary for reducing fluoride toxicity. Thirty rabbits, 2 months old, were divided into five groups. Group I animals received 1 mg/l fluoride and 0.11% calcium diet; groups II and III received 10 mg/l fluoride and diet with 0.11% or 2.11% calcium, respectively; and groups IV and V received 150 mg/l fluoride and diet with 2.11% or 0.11% calcium, respectively. Analysis of bone density, ash content, fluoride, calcium, phosphorus, and Ca:P molar ratio levels after 6 months of treatment indicated that animals that received high fluoride with low-calcium diet showed significant detrimental changes in physicochemical properties of bone. Animals that received fluoride with high calcium intake showed notable amelioration of the impact of calcium on fluoride-induced changes in bone. The degree of fluoride-induced characteristic changes in structural properties such as crystalline size, crystallinity, and crystallographic "c"-axis length of bone apatite cells was also assessed by X-ray diffraction and Fourier transform infrared studies. X-ray images showed bone deformity changes such as transverse stress growth lines, soft tissue ossification, and calcification in different parts of bones as a result of high fluoride accumulation and the beneficial role of calcium intake on its control.

Water fluoridation: a critical review of the physiological effects of ingested fluoride as a public health intervention.

PubMed

Peckham, Stephen; Awofeso, Niyi

2014-01-01

Fluorine is the world's 13th most abundant element and constitutes 0.08% of the Earth crust. It has the highest electronegativity of all elements. Fluoride is widely distributed in the environment, occurring in the air, soils, rocks, and water. Although fluoride is used industrially in a fluorine compound, the manufacture of ceramics, pesticides, aerosol propellants, refrigerants, glassware, and Teflon cookware, it is a generally unwanted byproduct of aluminium, fertilizer, and iron ore manufacture. The medicinal use of fluorides for the prevention of dental caries began in January 1945 when community water supplies in Grand Rapids, United States, were fluoridated to a level of 1 ppm as a dental caries prevention measure. However, water fluoridation remains a controversial public health measure. This paper reviews the human health effects of fluoride. The authors conclude that available evidence suggests that fluoride has a potential to cause major adverse human health problems, while having only a modest dental caries prevention effect. As part of efforts to reduce hazardous fluoride ingestion, the practice of artificial water fluoridation should be reconsidered globally, while industrial safety measures need to be tightened in order to reduce unethical discharge of fluoride compounds into the environment. Public health approaches for global dental caries reduction that do not involve systemic ingestion of fluoride are urgently needed.

Effect of fluoride on growth and acid production by Streptococcus mutans in dental plaque.

PubMed Central

van der Hoeven, J S; Franken, H C

1984-01-01

The aim of this study was to measure the effect of fluoride on the production of organic acids by Streptococcus mutans in dental plaque. The effect was studied in a simplified model of dental plaque with gnotobiotic rats monoinfected with S. mutans Ny341. Adaptation of S. mutans to fluoride was induced by feeding one group of the rats on fluoride-containing diet and drinking water. No difference was found in the accumulation of S. mutans on the teeth between the fluoride-adapted and the control groups. However, there was a significant difference in the amount of lactic acid in metabolically resting plaque between the groups, lactic acid being lower in the fluoride-adapted plaque. At 5 min after a rinse containing 10% sucrose, a high level of lactic acid was found in plaque from animals not exposed to fluoride. Rinses containing 4 or 20 mM fluoride before the sucrose rinse significantly inhibited the lactic acid production in the control group. In the plaque from rats on fluoridated diet and drinking water the sucrose-induced production of lactic acid was not inhibited by a 4 mM fluoride rinse. Moreover, the production of lactic acid in the fluoride-adapted plaque was prolonged. The results indicate that due to fluoride adaptation the inhibition of acid production is unlikely to be important for the caries-preventive action of fluoride. PMID:6746094

Water Fluoridation: A Critical Review of the Physiological Effects of Ingested Fluoride as a Public Health Intervention

PubMed Central

2014-01-01

Fluorine is the world's 13th most abundant element and constitutes 0.08% of the Earth crust. It has the highest electronegativity of all elements. Fluoride is widely distributed in the environment, occurring in the air, soils, rocks, and water. Although fluoride is used industrially in a fluorine compound, the manufacture of ceramics, pesticides, aerosol propellants, refrigerants, glassware, and Teflon cookware, it is a generally unwanted byproduct of aluminium, fertilizer, and iron ore manufacture. The medicinal use of fluorides for the prevention of dental caries began in January 1945 when community water supplies in Grand Rapids, United States, were fluoridated to a level of 1 ppm as a dental caries prevention measure. However, water fluoridation remains a controversial public health measure. This paper reviews the human health effects of fluoride. The authors conclude that available evidence suggests that fluoride has a potential to cause major adverse human health problems, while having only a modest dental caries prevention effect. As part of efforts to reduce hazardous fluoride ingestion, the practice of artificial water fluoridation should be reconsidered globally, while industrial safety measures need to be tightened in order to reduce unethical discharge of fluoride compounds into the environment. Public health approaches for global dental caries reduction that do not involve systemic ingestion of fluoride are urgently needed. PMID:24719570

PRODUCTION OF PLUTONIUM FLUORIDE FROM BISMUTH PHOSPHATE PRECIPITATE CONTAINING PLUTONIUM VALUES

DOEpatents

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

1961-05-01

A process is given for separating plutonium from fission products present on a bismuth phosphate carrier. The dried carrier is first treated with hydrogen fluoride at between 500 and 600 deg C whereby some fission product fluorides volatilize away from plutonium tetrafluoride, and nonvolatile fission product fluorides are formed then with anhydrous fluorine at between 400 and 500 deg C. Bismuth and plutonium distill in the form of volatile fluorides away from the nonvolatile fission product fluorides. The bismuth and plutonium fluorides are condensed at below 290 deg C.

Chemico-therapeutic approach to prevention of dental caries. [using stannous fluoride gel

NASA Technical Reports Server (NTRS)

Shannon, I. L.

1975-01-01

The program of chemical preventive dentistry is based primarily upon the development of a procedure for stabilizing stannous fluoride in solution by forcing it into glycerin. New topical fluoride treatment concentrates, fluoride containing gels and prophylaxis pastes, as well as a completely stable stannous fluoride dentifrice are made possible by the development of a rather complicated heat application method to force stannous fluoride into solution in glycerin. That the stannous fluoride is clinically effective in such a preparation is demonstrated briefly on orthodontic patients.

Effects of fluoridated milk on root dentin remineralization.

PubMed

Arnold, Wolfgang H; Heidt, Bastian A; Kuntz, Sebastian; Naumova, Ella A

2014-01-01

The prevalence of root caries is increasing with greater life expectancy and number of retained teeth. Therefore, new preventive strategies should be developed to reduce the prevalence of root caries. The aim of this study was to investigate the effects of fluoridated milk on the remineralization of root dentin and to compare these effects to those of sodium fluoride (NaF) application without milk. Thirty extracted human molars were divided into 6 groups, and the root cementum was removed from each tooth. The dentin surface was demineralized and then incubated with one of the following six solutions: Sodium chloride NaCl, artificial saliva, milk, milk+2.5 ppm fluoride, milk+10 ppm fluoride and artificial saliva+10 ppm fluoride. Serial sections were cut through the lesions and investigated with polarized light microscopy and quantitative morphometry, scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). The data were statistically evaluated using a one-way ANOVA for multiple comparisons. The depth of the lesion decreased with increasing fluoride concentration and was the smallest after incubation with artificial saliva+10 ppm fluoride. SEM analysis revealed a clearly demarcated superficial remineralized zone after incubation with milk+2.5 ppm fluoride, milk+10 ppm fluoride and artificial saliva+10 ppm fluoride. Ca content in this zone increased with increasing fluoride content and was highest after artificial saliva+10 ppm fluoride incubation. In the artificial saliva+10 ppm fluoride group, an additional crystalline layer was present on top of the lesion that contained elevated levels of F and Ca. Incubation of root dentin with fluoridated milk showed a clear effect on root dentin remineralization, and incubation with NaF dissolved in artificial saliva demonstrated a stronger effect.

Evaluation of salivary fluoride retention from a new high fluoride mouthrinse.

PubMed

Mason, Stephen C; Shirodaria, Soha; Sufi, Farzana; Rees, Gareth D; Birkhed, Dowen

2010-11-01

To evaluate salivary fluoride retention from a new high fluoride daily use mouthrinse over a 120 min period. Sixteen subjects completed a randomised single-blind, four-treatment cross-over trial. Sensodyne® Pronamel® mouthrinse (A) contained 450 ppm fluoride; reference products were Colgate® Fluorigard® (B), Listerine® Total Care (C) and Listerine Softmint Sensation (D) containing 225, 100 and 0 ppm fluoride respectively. Salivary fluoride retention was monitored ex vivo after a single supervised use of test product (10 mL, 60 s). Samples were collected at 0, 1, 3, 5, 15, 30, 60 and 120 min post-rinse, generating fluoride clearance curves from which the area under the curve (AUC) was calculated. Differences in salivary fluoride concentrations for each product were analysed using ANCOVA at each time point using a 5% significance level, as well as lnAUC for the periods 0-120, 0-1, 1-15, 15-60 and 60-120 min. Pairwise comparisons between all treatment groups were performed. Salivary fluoride levels for A-C peaked immediately following use. Fluoride levels were statistically significantly higher for A versus B-D (p≤ 0.004), linear dose responses were apparent. AUC(0-120) was statistically significantly greater for A than for B (p = 0.035), C (p< 0.0001) and D (p< 0.0001). Post-hoc comparisons of lnAUC for the remaining time domains showed fluoride retention from A was statistically significantly greater versus B-D (p< 0.0001). Single-use treatment with the new mouthrinse containing 450 ppm fluoride resulted in statistically significantly higher salivary fluoride levels throughout the 120 min test period. Total fluoride retention (AUC(0-120)) was also statistically significantly greater versus comparator rinse treatments. Copyright © 2010 Elsevier Ltd. All rights reserved.

Fluoride Increase in Saliva and Dental Biofilm due to a Meal Prepared with Fluoridated Water or Salt: A Crossover Clinical Study.

PubMed

Lima, Carolina V; Tenuta, Livia M A; Cury, Jaime A

2018-06-07

Knowledge about fluoride delivery to oral fluids from foods cooked with fluoridated water and salt is scarce, and no study has evaluated fluoride concentrations in saliva or biofilm during meal consumption. In this randomized double-blind crossover study, 12 volunteers ingested meals (rice, beans, meat, and legumes) prepared with nonfluoridated water and salt (control group), fluoridated water (0.70 mg F/L; water group), and fluoridated salt (183.7 mg F/kg; salt group). Whole saliva was collected before meal ingestion, during mastication, and up to 2 h after meal ingestion. Dental biofilm was collected before and immediately after meal ingestion. Fluoride concentrations in saliva and dental biofilm were determined by an ion-specific electrode. The mean (±standard deviation; n = 4) fluoride concentrations in meals prepared for the control, water, and salt groups were 0.039 ± 0.01, 0.43 ± 0.04, and 1.71 ± 0.32 μg F/g, respectively. The three groups had significantly different fluoride concentrations in saliva collected during mastication (p < 0.0001) and after meal ingestion (p < 0.04; salt > water > control). The fluoride concentration in saliva returned to baseline 30 min after meal ingestion in the water group but remained high for up to 2 h in the salt group (p = 0.002). The fluoride concentration in biofilm fluid differed only between the salt and control groups (p = 0.008). The mastication of foods cooked with fluoridated water and salt increases fluoride concentrations in oral fluids and may contribute to the local effect of these community-based fluoride interventions on caries control. © 2018 S. Karger AG, Basel.

Salt fluoridation and oral health.

PubMed

Marthaler, Thomas M

2013-11-01

The aim of this paper is to make known the potential of fluoridated salt in community oral health programs, particularly in South Eastern Europe. Since 1922, the addition of iodine to salt has been successful in Switzerland. Goiter is virtually extinct. By 1945, the caries-protective effect of fluorides was well established. Based on the success of water fluoridation, a gynecologist started adding of fluoride to salt. The sale of fluoridated salt began in 1956 in the Swiss Canton of Zurich, and several other cantons followed suit. Studies initiated in the early seventies showed that fluoride, when added to salt, inhibits dental caries. The addition of fluoride to salt for human consumption was officially authorized in 1980-82. In Switzerland 85% of domestic salt consumed is fluoridated and 67% in Germany. Salt fluoridation schemes are reaching more than one hundred million in Mexico, Colombia, Peru and Cuba. The cost of salt fluoridation is very low, within 0.02 and 0.05 € per year and capita. Children and adults of the low socio-economic strata tend to have substantially more untreated caries than higher strata. Salt fluoridation is by far the cheapest method for improving oral health. Salt fluoridation has cariostatic potential like water fluoridation (caries reductions up to 50%). In Europe, meaningful percentages of users have been attained only in Germany (67%) and Switzerland (85%). In Latin America, there are more than 100 million users, and several countries have arrived at coverage of 90 to 99%. Salt fluoridation is by far the cheapest method of caries prevention, and billions of people throughout the world could benefit from this method. Copyright © 2013 by Academy of Sciences and Arts of Bosnia and Herzegovina.

Salt fluoridation--an alternative in automatic prevention of dental caries.

PubMed

Marthaler, T M; Petersen, P E

2005-12-01

Despite great improvements in terms of reduced prevalence and amount of dental caries in populations worldwide, problems still persist particularly among the underprivileged groups of both developed and developing countries. Research and practical experience gained in several countries have demonstrated however, that dental caries can be prevented effectively through establishment of fluoride programmes. Water fluoridation, salt fluoridation, milk fluoridation and use of affordable fluoridated toothpastes play the major roles in public health. The present paper outlines the relevance and some practical aspects in relation to implementation of salt fluoridation programmes. The World Health Organisation Oral Health Programme provides technical assistance to countries in the process of planning, implementing and evaluating salt fluoridation projects.

Fluoride’s Effects on the Formation of Teeth and Bones, and the Influence of Genetics

PubMed Central

Everett, E.T.

2011-01-01

Fluorides are present in the environment. Excessive systemic exposure to fluorides can lead to disturbances of bone homeostasis (skeletal fluorosis) and enamel development (dental/enamel fluorosis). The severity of dental fluorosis is also dependent upon fluoride dose and the timing and duration of fluoride exposure. Fluoride’s actions on bone cells predominate as anabolic effects both in vitro and in vivo. More recently, fluoride has been shown to induce osteoclastogenesis in mice. Fluorides appear to mediate their actions through the MAPK signaling pathway and can lead to changes in gene expression, cell stress, and cell death. Different strains of inbred mice demonstrate differential physiological responses to ingested fluoride. Genetic studies in mice are capable of identifying and characterizing fluoride-responsive genetic variations. Ultimately, this can lead to the identification of at-risk human populations who are susceptible to the unwanted or potentially adverse effects of fluoride action and to the elucidation of fundamental mechanisms by which fluoride affects biomineralization. PMID:20929720

Is the fluoride intake by diet and toothpaste in children living in tropical semi-arid city safe?

PubMed

Oliveira, Priscila Ferreira Torres de; Cury, Jaime Aparecido; Lima, Carolina Veloso; Vale, Glauber Campos; Lima, Marina de Deus Moura de; Moura, Lúcia de Fátima Almeida de Deus; Moura, Marcoeli Silva de

2018-01-01

Data about total fluoride intake in children living in a tropical semi-arid climate city is scarce, thus we conducted this study. Fifty-eight children aged two to five years, living in a Brazilian tropical city with optimally fluoridated water were selected. Dietary samples were collected using the duplicate diet method on two non-consecutive days in the children's home toothpaste was determined by subtracting the amount of fluoride recovered after brushing from the amount placed on the toothbrush. The mean total dose (SD) of fluoride intake was 0.043(0.016) mg F·kg-1·d-1, with the major (60.6%) contribution from water. The factors associated with the ingestion of fluoride from toothpaste were fluoride concentration of the toothpaste (p = 0.03) and the use of kids toothpaste (p = 0.02). The findings suggest that children have a low fluoride intake, measured by at-home meals and use of fluoride toothpaste; drinking water is the main source of fluoride ingestion.

Sodium trimetaphosphate enhances the effect of 250 p.p.m. fluoride toothpaste against enamel demineralization in vitro.

PubMed

Missel, Emilene M C; Cunha, Robson F; Vieira, Ana E M; Cruz, Nathália V S; Castilho, Flavia C N; Delbem, Alberto C B

2016-08-01

This in vitro study investigated the effect of sodium trimetaphosphate (TMP), added to toothpaste containing 250 p.p.m. fluoride, on enamel demineralization. Bovine enamel blocks (n = 96) were subjected to five pH cycles over a 7-d period and treatment with suspensions of toothpastes containing 0, 250, 500, and 1,100 p.p.m. fluoride (as sodium fluoride), as well as with 250 p.p.m. fluoride containing TMP at 0.25, 0.5, 1.0, and 3.0%. Treatment with toothpaste suspensions was performed under agitation twice a day, for 1 min. Surface and cross-sectional hardness, and fluoride firmly bound to enamel, were quantified. Data were subjected to one-way anova, followed by Tukey's test. Low-fluoride toothpastes containing TMP at 0.25-1.0% resulted in enamel mineral loss similar to that seen for the toothpaste containing 1,100 p.p.m. fluoride. Also, the addition of TMP to the toothpaste containing 250 p.p.m. fluoride promoted enamel fluoride concentrations similar to those obtained for the 500 p.p.m. fluoride group. The toothpaste containing 250 p.p.m. fluoride and 0.25% TMP led to the lowest mineral loss among all groups. It was concluded that the addition of as little as 0.25% TMP to a toothpaste containing 250 p.p.m. fluoride can reduce enamel demineralization to levels similar to those seen for a conventional toothpaste containing 1,100 p.p.m. fluoride, in vitro. © 2016 Eur J Oral Sci.

Fluoride concentration in dentine as a biomarker of fluoride intake in European roe deer (Capreolus capreolus) - an electron-microprobe study.

PubMed

Richter, Heiko; Kierdorf, Uwe; Richards, Alan; Melcher, Frank; Kierdorf, Horst

2011-08-01

Fluoride concentration in dentine has been recommended as the best marker for the level of chronic fluoride intake and the most suitable indicator of an individual's total body burden of fluoride. We analysed fluoride concentrations in the dentine of cheek teeth of European roe deer from fluoride-polluted habitats to retrospectively assess the level of fluoride uptake into the tissue. Thereby, we tested the hypothesis of the existence of mechanisms that limit fluoride intake of individuals and fluoride exposure of forming dental hard tissues during the late foetal and early postnatal periods in the species. Using electron-microprobe analysis, fluoride profiles were obtained on sectioned P(4)s, M(1)s, and M(3)s from individuals exhibiting pronounced dental fluorosis. Fluoride concentrations were compared between early formed (peripheral) and late-formed (juxtapulpal) dentine both within single teeth and amongst the three different teeth studied. Peripheral dentine of the M(1), which is formed during the late foetal and early postnatal periods, exhibited markedly lower fluoride concentrations than juxtapulpal dentine of the same tooth and both, peripheral and juxtapulpal dentine of P(4) and M(3) that are formed post-weaning. Our study provides strong support for the hypothesis that in the European roe deer the prenatal and early postnatal (pre-weaning) stages of dental development are (largely) protected against exposure to excess fluoride. This is attributed to the operation of certain protective mechanisms during these periods. Copyright © 2011 Elsevier Ltd. All rights reserved.

Critical factors determining fluoride concentration in tea leaves produced from Anhui province, China.

PubMed

Cai, Huimei; Zhu, Xiaohui; Peng, Chuanyi; Xu, Wei; Li, Daxiang; Wang, Yijun; Fang, Shihui; Li, Yeyun; Hu, Shaode; Wan, Xiaochun

2016-09-01

This study investigated the fluoride present in tea plants (Camellia sinensis (L.) O. Kuntze) and its relationship to soils, varieties, seasons and tea leaf maturity. The study also explored how different manufacturing processes affect the leaching of fluoride into tea beverages. The fluoride concentration in the tea leaves was significantly correlate to the concentration of water-soluble fluoride in the soil. Different tea varieties accumulated different levels of fluoride, with varieties, Anji baicha having the highest and Nongkang zao having the lowest fluoride concentration. In eight different varieties of tea plant harvested over three tea seasons, fluoride concentration were highest in the summer and lowest in the spring in china. The fluoride concentration in tea leaves was directly related to the maturity of the tea leaves at harvest. Importantly, the tea manufacturing process did not introduced fluoride contamination. The leaching of fluoride was 6.8% and 14.1% higher in black and white tea, respectively, than in fresh tea leaves. The manufacturing step most affecting the leaching of fluoride into tea beverage was withering used in white, black and oolong tea rather than rolling or fermentation. The exposure and associated health risks for fluoride concentration in infusions of 115 commercially available teas from Chinese tea markets was determined. The fluoride concentration ranged from 5.0 to 306.0mgkg(-1), with an average of 81.7mgkg(-1). The hazard quotient (HQ) of these teas indicated that there was no risk of fluorosis from drinking tea, based on statistical analysis by Monte Carlo simulation. Copyright © 2016 Elsevier Inc. All rights reserved.

Fluoride exposure and indicators of thyroid functioning in the Canadian population: implications for community water fluoridation

PubMed Central

Barberio, Amanda M; Hosein, F Shaun; Quiñonez, Carlos; McLaren, Lindsay

2017-01-01

Background There are concerns that altered thyroid functioning could be the result of ingesting too much fluoride. Community water fluoridation (CWF) is an important source of fluoride exposure. Our objectives were to examine the association between fluoride exposure and (1) diagnosis of a thyroid condition and (2) indicators of thyroid functioning among a national population-based sample of Canadians. Methods We analysed data from Cycles 2 and 3 of the Canadian Health Measures Survey (CHMS). Logistic regression was used to assess associations between fluoride from urine and tap water samples and the diagnosis of a thyroid condition. Multinomial logistic regression was used to examine the relationship between fluoride exposure and thyroid-stimulating hormone (TSH) level (low/normal/high). Other available variables permitted additional exploratory analyses among the subset of participants for whom we could discern some fluoride exposure from drinking water and/or dental products. Results There was no evidence of a relationship between fluoride exposure (from urine and tap water) and the diagnosis of a thyroid condition. There was no statistically significant association between fluoride exposure and abnormal (low or high) TSH levels relative to normal TSH levels. Rerunning the models with the sample constrained to the subset of participants for whom we could discern some source(s) of fluoride exposure from drinking water and/or dental products revealed no significant associations. Conclusion These analyses suggest that, at the population level, fluoride exposure is not associated with impaired thyroid functioning in a time and place where multiple sources of fluoride exposure, including CWF, exist. PMID:28839078

[Effect of fluoride on human hypothalamus-hypophysis-testis axis hormones].

PubMed

Hao, Pengfei; Ma, Xiaoying; Cheng, Xuemin; Ba, Yue; Zhu, Jingyuan; Cui, Liuxin

2010-01-01

To study of endocrine disturbing effect of fluoride on human hypothalamus-hypophysis-testis axis hormones. Sunying County, Kaifeng City was selected as polluted district which the fluoride in drinking water was 3.89 mg/L, and Shenlilou county was selected as control district which the fluoride was less than 1.0 mg/L. 150 individual lived there more than 5 years were srlected randomly. And investigated by medical examination, then blood and urine sample were collected, and the serum level of gonadotropin-releasing hormone (GnRH), luteinizing hormone (LH), testosterone (T) and estradiol (E2) were measured by RIA method, and the urine level of fluoride were measured. Other than that, the concentration of fluoride in the water, food, soil and air were detected by the standard methods. The concentrations of fluoride in the water, food and soil of the fluoride polluted district were significantly higher than those of control district (P < 0.05), and the concentration fluoride in the air of two district were not found. There was no significant difference of serum level of GnRH between fluoride polluted district and control district (P > 0.05). The serum level of LH in men of fluoride polluted district was significantly higher than that of control group (P < 0.05), and the serum level of T in men of fluoride polluted district was significantly less than that of control group (P < 0.05). There was no significant difference of serum level of LH between fluoride polluted district and control district (P > 0.05), and the serum level of T in women of fluoride polluted district was significantly higher than that of control group (P < 0.05). There was no significant difference of serum level of E2 between fluoride polluted district and control district (P > 0.05). Fluoride could effect hormone levels of each layer of the hypothalamus-hypophysis-testis axis, and show the reproductive endocrine disturbing effects. The reproductive endocrine disturbing effects of male maybe more severe than those of female.

49 CFR 173.163 - Hydrogen fluoride.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 49 Transportation 2 2013-10-01 2013-10-01 false Hydrogen fluoride. 173.163 Section 173.163... Hydrogen fluoride. (a) Hydrogen fluoride (hydrofluoric acid, anhydrous) must be packaged as follows: (1) In... filling ratio of 0.84. (b) A cylinder removed from hydrogen fluoride service must be condemned in...

49 CFR 173.163 - Hydrogen fluoride.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 49 Transportation 2 2012-10-01 2012-10-01 false Hydrogen fluoride. 173.163 Section 173.163... Hydrogen fluoride. (a) Hydrogen fluoride (hydrofluoric acid, anhydrous) must be packaged as follows: (1) In... filling ratio of 0.84. (b) A cylinder removed from hydrogen fluoride service must be condemned in...

49 CFR 173.163 - Hydrogen fluoride.

Code of Federal Regulations, 2014 CFR

2014-10-01

... 49 Transportation 2 2014-10-01 2014-10-01 false Hydrogen fluoride. 173.163 Section 173.163... Hydrogen fluoride. (a) Hydrogen fluoride (hydrofluoric acid, anhydrous) must be packaged as follows: (1) In... filling ratio of 0.84. (b) A cylinder removed from hydrogen fluoride service must be condemned in...

FLUORIDATION CHEMISTRY: EQUILIBRIA AND KINETICS OF FLUORIDE AND FLUORO-COMPLEXES

EPA Science Inventory

The most common fluoridating agents used by major American waterworks are hexafluorosilicic acid (H2SiF6) and sodium hexxafluorosilicate (Na2SiF6). According to the 1992 Water Fluoridation Census where 10,002 utilities responded affirmatively to fluoridating their water, 59
% ...

49 CFR 173.163 - Hydrogen fluoride.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 49 Transportation 2 2010-10-01 2010-10-01 false Hydrogen fluoride. 173.163 Section 173.163... Hydrogen fluoride. (a) Hydrogen fluoride (hydrofluoric acid, anhydrous) must be packaged as follows: (1) In... filling ratio of 0.84. (b) A cylinder removed from hydrogen fluoride service must be condemned in...

49 CFR 173.163 - Hydrogen fluoride.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 49 Transportation 2 2011-10-01 2011-10-01 false Hydrogen fluoride. 173.163 Section 173.163... Hydrogen fluoride. (a) Hydrogen fluoride (hydrofluoric acid, anhydrous) must be packaged as follows: (1) In... filling ratio of 0.84. (b) A cylinder removed from hydrogen fluoride service must be condemned in...

Fluoridation and Defluoridation. Training Module 2.230.2.77.

ERIC Educational Resources Information Center

McMullen, L. D.

This document is an instructional module package prepared in objective form for use by an instructor familiar with fluoridation and fluoride feeding equipment. Enclosed are objectives, an instructor guide, student handouts and transparency masters. The module considers the principles and purposes of fluoridation, methods of feeding fluoride,…

21 CFR 355.70 - Testing procedures for fluoride dentifrice drug products.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 5 2010-04-01 2010-04-01 false Testing procedures for fluoride dentifrice drug... Procedures § 355.70 Testing procedures for fluoride dentifrice drug products. (a) A fluoride dentifrice drug... tests: Enamel solubility reduction or fluoride enamel uptake. The testing procedures for these...

21 CFR 355.70 - Testing procedures for fluoride dentifrice drug products.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 5 2011-04-01 2011-04-01 false Testing procedures for fluoride dentifrice drug... Procedures § 355.70 Testing procedures for fluoride dentifrice drug products. (a) A fluoride dentifrice drug... tests: Enamel solubility reduction or fluoride enamel uptake. The testing procedures for these...

Design Manual: Removal of Fluoride from Drinking Water ...

EPA Pesticide Factsheets

This document is an updated version of the Design Manual: Removal of Fluoride from Drinking Water Supplies by Activated Alumina (Rubel, 1984). The manual is an in-depth presentation of the steps required to design and operate a fluoride removal plant using activated alumina (AA), which is a reliable and cost-effective process for treating excess fluoride from drinking water supplies. Design Manual on removing fluoride from drinking water to support the fluoride MCL - manual

Copper Mediated Fluorination of Aryl Iodides

PubMed Central

Fier, Patrick S.; Hartwig, John F.

2012-01-01

The synthesis of aryl fluorides has been a topic of considerable interest because of the importance of aryl fluorides in pharmaceuticals, agrochemicals and materials. The stability, reactivity and biological properties of aryl fluorides can be distinct from those of the corresponding arenes. Methods for the synthesis of aryl fluorides, however, are limited. We report the conversion of a diverse set of aryl iodides to the corresponding aryl fluorides. This reaction occurs with a cationic copper reagent and silver fluoride. Preliminary results suggest this reaction is enabled by a facile reductive elimination from a cationic aryl copper(III) fluoride. PMID:22709145

Fluoride Binding to Dental Biofilm Bacteria: Synergistic Effect with Calcium Questioned.

PubMed

Nóbrega, Diego Figueiredo; Leitão, Tarcísio Jorge; Cury, Jaime Aparecido; Tenuta, Livia Maria Andaló

2018-06-06

It has been suggested that fluoride binding to dental biofilm is enhanced when more bacterial calcium binding sites are available. However, this was only observed at high calcium and fluoride concentrations (i.e., when CaF2 precipitation may have occurred). We assessed fluoride binding to Streptococcus mutans pellets treated with calcium and fluoride at concentrations allowing CaF2 precipitation or not. Increasing calcium concentration resulted in a linear increase (p < 0.01) in fluoride concentration only in the pellets in which CaF2 precipitated. The results suggest that CaF2 precipitation, rather than bacterially bound fluoride, is responsible for the increase in fluoride binding to dental biofilm with the increase in calcium availability. © 2018 S. Karger AG, Basel.

Small Molecule Fluoride Toxicity Agonists

PubMed Central

Nelson1, James W.; Plummer, Mark S.; Blount, Kenneth F.; Ames, Tyler D.; Breaker, Ronald R.

2015-01-01

SUMMARY Fluoride is a ubiquitous anion that inhibits a wide variety of metabolic processes. Here we report the identification of a series of compounds that enhance fluoride toxicity in Escherichia coli and Streptococcus mutans. These molecules were isolated by using a high-throughput screen (HTS) for compounds that increase intracellular fluoride levels as determined via a fluoride riboswitch-reporter fusion construct. A series of derivatives were synthesized to examine structure-activity relationships, leading to the identification of compounds with improved activity. Thus, we demonstrate that small molecule fluoride toxicity agonists can be identified by HTS from existing chemical libraries by exploiting a natural fluoride riboswitch. In addition, our findings suggest that some molecules might be further optimized to function as binary antibacterial agents when combined with fluoride. PMID:25910244

Corrosion Behavior of Titanium Grade 7 in Fluoride-Containing NaCl Brines

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

Lian, T; Whalen, M T; Wong, L

2004-10-25

The effects of fluoride on the corrosion behavior of Titanium Grade 7 (0.12-0.25% Pd) have been investigated. Up to 0.1 mol/L fluoride was added to the NaCl brines at 95 C, and three pH values of 4, 8, and 11 were selected for studying pH dependence of fluoride effects. It was observed that fluoride significantly altered the anodic polarization behavior, at all three pH values of 4, 8, and 11. Under acidic condition fluoride caused active corrosion. The corrosion of Titanium grade 7 was increased by three orders of magnitude when a 0.1 mol/L fluoride was added to the NaClmore » brines at pH 4, and the Pd ennoblement effect was not observed in acidic fluoride-containing environments. The effects of fluoride were reduced significantly when pH was increased to 8 and above.« less

Global water fluoridation: what is holding us back?

PubMed

Botchey, Sally-Ann; Ouyang, Jing; Vivekanantham, Sayinthen

2015-01-01

Artificial water fluoridation was introduced more than 60 y ago as a public health intervention to control dental caries. Despite wide recommendations for its use from the World Health Organization (WHO) and studies showing the benefits of water fluoridation, many countries have opted out. Currently, only 25 countries, including the United Kingdom, the United States, and Australia have schemes for artificial water fluoridation. The issues faced in efforts to promote the global uptake of water fluoridation and the factors that affect the decision to implement it are unique in both developed and developing countries and must be explored. This article addresses the benefits and challenges of artificial water fluoridation. Further, it tackles the complexities faced with uptake of water fluoridation globally, such as ethical and political controversies and the use of alternative fluoride therapies. Potential future strategies to encourage the uptake of artificial water fluoridation are also discussed.

Controlling the fluoride dosage in a patient with compromised salivary function.

PubMed

Eichmiller, Frederick C; Eidelman, Naomi; Carey, Clifton M

2005-01-01

High-concentration topical fluorides are used commonly to with compromised salivary function due to irradiation and chemotherapy. The authors describe a 50-year-old man with previously treated cancer who was using tray-applied topical fluoride gel. He complained of gastric symptoms, difficulty in swallowing, leg muscle soreness and knee joint soreness. A computed tomographic scan revealed thickening of the esophageal walls. An upper endoscopy revealed abnormal motility. The motility test indicated high-amplitude peristalsis and hypertensive lower esophageal sphincter, and urine testing indicated high levels of systemic fluoride. The patient's fluoride regimen was altered, and within a short period his urinary fluoride levels returned to normal and his symptoms resolved. Clinicians prescribing home-applied high-concentration fluorides need to be cognizant of the symptoms of fluoride toxicity, carefully monitor the patient's compliance with the treatment regimen, and adjust the dosage or mode of application to control the total ingested dose of fluoride.

Water fluoridation and oral health.

PubMed

Harding, Máiréad Antoinette; O'Mullane, Denis Martin

2013-11-01

Water fluoridation, is the controlled addition of fluoride to the water supply, with the aim of reducing the prevalence of dental caries. Current estimates suggest that approximately 370 million people in 27 countries consume fluoridated water, with an additional 50 million consuming water in which fluoride is naturally occurring. A pre-eruptive effect of fluoride exists in reducing caries levels in pit and fissure surfaces of permanent teeth and fluoride concentrated in plaque and saliva inhibits the demineralisation of sound enamel and enhances the remineralisation of demineralised enamel. A large number of studies conducted worldwide demonstrate the effectiveness of water fluoridation. Objections to water fluoridation have been raised since its inception and centre mainly on safety and autonomy. Systematic reviews of the safety and efficacy of water fluoridation attest to its safety and efficacy; dental fluorosis identified as the only adverse outcome. Water fluoridation is an effective safe means of preventing dental caries, reaching all populations, irrespective of the presence of other dental services. Regular monitoring of dental caries and fluorosis is essential particularly with the lifelong challenge which dental caries presents. Copyright © 2013 by Academy of Sciences and Arts of Bosnia and Herzegovina.

Fluoridation advocacy in Queensland: a long and winding road.

PubMed

Akers, Harry Francis; Foley, Michael Anthony

2012-10-01

By 1977, all Australian states and mainland territories, with the exception of Queensland, had widely implemented adjusted water fluoridation. This disparity in public health policy persisted until 2008. This study analyses the sociopolitical and socioeconomic backgrounds that underpinned the repeal of the Fluoridation of Public Water Supplies Act (1963) and its replacement with the Water Fluoridation Act (2008). The authors used a literature review and historic method. References are in the public domain. The devolution, without funding, of a discretionary local authority power to fluoridate contributed to the perennial low fluoridation status in Queensland. A window of opportunity for fluoridation advocates opened between 2003 and 2008. Now that 87% of Queenslanders have access to optimally fluoridated water, Queensland premier Anna Bligh has largely delivered on a promise made in 2007 to fluoridate water supplies across the state. The implementation of adjusted water fluoridation requires not only political stability and resolve, but also centralised authority. The last of these factors must embrace the decision, the funding and the indemnity. State control over water-related infrastructure and water treatment enhances prospects for fluoridation. The roles of opinion polls, internal advisers and departmental figures are also confirmed. Political repercussions were minimal. © 2012 FDI World Dental Federation.

Fluoride in drinking water and human urine in Southern Haryana, India.

PubMed

Singh, Bhupinder; Gaur, Shalini; Garg, V K

2007-06-01

The objective of this study was to determine the fluoride content in drinking water and urine samples of adolescent males aged 11-16 years living in Southern Haryana, India. A total of 30 drinking water sources in the studied habitations were assessed for fluoride contamination. Fluoride was estimated in the urine of 400 male children randomly selected from these habitations. The fluoride concentration in drinking water and urine samples was determined using USEPA fluoride ion selective electrode method. The mean fluoride concentration in drinking water samples of Pataudi, Haily Mandi and Harsaru villages was 1.68+/-0.35, 3.22+/-1.18 and 1.78+/-0.12 mg/l, respectively. The mean urinary fluoride concentration was 2.26+/-0.024 mg/l at Pataudi, 2.48+/-0.77 mg/l at Haily Mandi and 2.43+/-0.84 mg/l at Harsaru village. The higher fluoride levels in the urine of children may be associated to higher fluoride levels in drinking water. The accuracy of measurements was assessed with known addition method in water and urine. Mean fluoride recovery was 98.0 and 99.1% in water and urine. The levels obtained were reproducible with in +/-3% error limit.

Development of a sustained fluoride delivery system.

PubMed

Baturina, Olga; Tufekci, Eser; Guney-Altay, Ozge; Khan, Shadeed M; Wnek, Gary E; Lindauer, Steven J

2010-11-01

To develop a novel delivery system by which fluoride incorporated into elastomeric rings, such as those used to ligate orthodontic wires, will be released in a controlled and constant manner. Polyethylene co-vinyl acetate (PEVA) was used as the model elastomer. Samples (N = 3) were prepared by incorporating 0.02 to 0.4 g of sodium fluoride (NaF) into previously prepared PEVA solution. Another group of samples prepared in the same manner were additionally dip-coated in PEVA to create an overcoat. Fluoride release studies were conducted in vitro using an ion selective electrode over a period of 45 days. The amount of fluoride released was compared to the optimal therapeutic dose of 0.7 microg F(-)/ring/d. Only coated samples with the highest fluoride content (group D, 0.4 g of NaF) were able to release fluoride at therapeutic levels. When fluoride release from coated and uncoated samples with the same amount of NaF were compared, it was shown that the dip-coating technique resulted in a fluoride release in a controlled manner while eliminating the initial burst effect. This novel fluoride delivery matrix provided fluoride release at a therapeutically effective rate and profile.

Fluoride bioaccumulation by hydroponic cultures of camellia (Camellia japonica spp.) and sugar cane (Saccharum officinarum spp.).

PubMed

Camarena-Rangel, Nancy; Rojas Velázquez, Angel Natanael; Santos-Díaz, María del Socorro

2015-10-01

The ability of hydroponic cultures of camellia and sugar cane adult plants to remove fluoride was investigated. Plants were grown in a 50% Steiner nutrient solution. After an adaptation period to hydroponic conditions, plants were exposed to different fluoride concentrations (0, 2.5, 5 and 10 mg L(-1)). Fluoride concentration in the culture medium and in tissues was measured. In sugar cane, fluoride was mainly located in roots, with 86% of it absorbed and 14% adsorbed. Sugar cane plants removed 1000-1200 mg fluoride kg(-1) dry weight. In camellia plants the highest fluoride concentration was found in leaf. Roots accumulated fluoride mainly through absorption, which was 2-5 times higher than adsorption. At the end of the experiment, fluoride accumulation in camellia plants was 1000-1400 mgk g(-1) dry weight. Estimated concentration factors revealed that fluoride bioaccumulation is 74-221-fold in camellia plants and 100-500-fold in sugar cane plants. Thus, the latter appear as a suitable candidate for removing fluoride from water due to their bioaccumulation capacity and vigorous growth rate; therefore, sugar cane might be used for phytoremediation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Comparison of Fluoridated Miswak and Toothbrushing with Fluoridated Toothpaste on Plaque Removal and Fluoride Release.

PubMed

Baeshen, Hosam; Salahuddin, Sabin; Dam, Robel; Zawawi, Khalid H; Birkhed, Dowen

2017-04-01

Dental caries and periodontal diseases are all induced by oral biofilm (dental plaque). This study was conducted to evaluate if fluoride-impregnated miswak is as effective in plaque removal and fluoride release as toothbrushing with fluoride toothpaste. This single-blind, randomized, crossover study was conducted at the Department of Cariology, University of Gothenburg, Gothenburg, Sweden, from February 2010 to January 2011. Fifteen healthy subjects participated in this study. The participants were instructed to use the following: (1) 0.5% NaF-impregnated miswak, (2) nonfluoridated miswak, (3) toothbrush with nonfluoride toothpaste, and (4) toothbrush with 1450 ppm fluoride toothpaste. Each method was used twice a day for 1 week after which plaque amount and fluoride concentration in resting saliva were measured. There was a 1-week washout period between each method. No significant difference between miswak and tooth-brushing was found regarding plaque removal on buccal and lingual surfaces. A somewhat higher fluoride concentration in resting saliva was found after using impregnated miswak when compared with toothbrushing with fluoride toothpaste (p < 0.05). Miswak and toothbrushing showed the same plaque removing effect on buccal and lingual surfaces. Miswak impregnated with 0.5% NaF resulted in a higher concentration of fluoride in saliva than brushing with 1450 ppm fluoride toothpaste. Miswak impregnated with 0.5% NaF and toothbrushing results in comparable plaque removal and about the same fluoride concentration in saliva even it was somewhat higher for impregnated miswak.

Effect of fluoride exposure on mRNA expression of cav1.2 and calcium signal pathway apoptosis regulators in PC12 cells.

PubMed

Liao, Qiuxia; Zhang, Rui; Wang, Xiaoyu; Nian, Weiwei; Ke, Lulu; Ouyang, Wei; Zhang, Zigui

2017-09-01

This study investigated the effects of fluoride exposure on the mRNA expression of Cav1.2 calcium signaling pathway and apoptosis regulatory molecules in PC12 cells. The viability of PC12 cell receiving high fluoride (5.0mM) and low fluoride (0.5mM) alone or fluoride combined with L-type calcium channel (LTCC) agonist/inhibitor (5umol/L FPL6417/2umol/L nifedipine) was detected using cell counting kit-8 at different time points (2, 4, 6, 8, 12, 10, and 24h). Changes in the cell configuration were observed after exposing the cells to fluoride for 24h. The expression levels of molecules related to the LTCC were examined, particularly, Cav1.2, c-fos, CAMK II, Bax, and Bcl-2. Fluoride poisoning induced severe cell injuries, such as decreased PC12 cell activity, enhanced cell apoptosis, high c-fos, CAMKII, and Bax mRNA expression levels. Bcl-2 expression level was also reduced. Meanwhile, high fluoride, high fluoride with FPL64176, and low fluoride with FPL64176 enhanced the Cav1.2 expression level. In contrast, low fluoride, high fluoride with nifedipine, and low fluoride with nifedipine reduced the Cav1.2 expression level. Thus, Cav1.2 may be an important molecular target for the fluorosis treatment, and the LTCC inhibitor nifedipine may be an effective drug for fluorosis. Copyright © 2017 Elsevier B.V. All rights reserved.

Study on fluoride emission from soils at high temperature related to brick-making process.

PubMed

Xie, Z M; Wu, W H; Xu, J M

2003-02-01

Characteristics of fluoride emission from 12 soils at temperatures of 400-1,100 degrees C related to the brick-making process were studied. The results obtained in this study indicate that fluoride emission as gaseous HF and SiF4 was related to the firing temperature, soil total fluoride content, soil composition and calcium compounds added to soils. Soils began to release fluoride at temperatures between 500 and 700 degrees C. Marked increases of the average fluoride mission rate from 57.2% to 85.4% of soil total fluoride were noticed as the heating temperature was increased from 700 to 1,100 degrees C. It was found that the major proportion (over 50%) of the soil total fluoride was emitted from soils at approximate 800 degrees C. The amount of fluoride released into the atmosphere when heated depended on the total fluoride contents in the soils. Correlation analysis showed that the soil composition, such as cation exchange capacity, exchangeable calcium and CaCO3, had some influence on fluoride emission below 900 degrees C, but had no influence at temperatures above 900 degrees C. Addition of four calcium compounds (CaO, CaCO3, Ca(OH)2, and CaSO4) at 1.5% by weight raised the temperature at which fluoride began to be released to 700 degrees C. The greatest decrease in fluoride emission among the four calcium compound treatments was found with CaCO3.

Fluoride penetration from toothpastes into incipient enamel erosive lesions investigated using dynamic secondary ion mass spectrometry.

PubMed

Fowler, C E; Gracia, L; Edwards, M I; Brown, A; Rees, G D

2009-01-01

The primary aim of this study was to assess the utility of dynamic secondary ion mass spectrometry (DSIMS) as a convenient and sensitive technique for determining fluoride uptake and distribution into incipient human enamel erosive lesions in vitro. A secondary aim was to correlate the extent of lesion rehardening following treatment with a toothpaste slurry, with relative fluoride uptake determined by DSIMS. The final aim was to compare fluoride uptake by incipient lesions treated with toothpastes containing different sources of fluoride using DSIMS. Relative fluoride uptake into the surface and body of enamel erosive lesions was monitored by DSIMS as a function of fluoride concentration in a series of formulation-matched experimental pastes. Fluoride uptake into lesions that had been subjected to treatment with different toothpaste slurries in a single-treatment enamel lesion rehardening model was also determined, and its relationship with regard to the extent of rehardening and also the fluoride source investigated. Fluoride uptake by incipient erosive lesions treated with toothpastes containing NaF was quantitatively compared by DSIMS and found to be directly proportional to the fluoride concentration over the studied range (0-1400 ppm). Lesion repair observed in a single-treatment lesion rehardening model was positively correlated with the extent of fluoride uptake by the treated lesions. DSIMS was also able to show differences between commercial toothpastes containing different sources of fluoride and their ability to deliver the fluoride into the body of the lesion. The detrimental effect of sodium hexametaphosphate (NaHMP) present in Crest Pro-Health formulations previously reported in the single-treatment lesion rehardening model was also evident from the DSIMS elemental line scans obtained from the lesion cross-sections. DSIMS has been shown to be a powerful selective technique for quantifying relative fluoride uptake into enamel erosive lesions, and determining the extent and depth of lesion penetration. The relative efficacy of toothpastes containing fluoride from a variety of sources in the single-treatment lesion rehardening study is positively correlated with fluoride uptake and penetration determined by DSIMS.

4-phenylbutyrate Mitigates Fluoride-Induced Cytotoxicity in ALC Cells

PubMed Central

Suzuki, Maiko; Everett, Eric T.; Whitford, Gary M.; Bartlett, John D.

2017-01-01

Chronic fluoride over-exposure during pre-eruptive enamel development can cause dental fluorosis. Severe dental fluorosis is characterized by porous, soft enamel that is vulnerable to erosion and decay. The prevalence of dental fluorosis among the population in the USA, India and China is increasing. Other than avoiding excessive intake, treatments to prevent dental fluorosis remain unknown. We previously reported that high-dose fluoride induces endoplasmic reticulum (ER) stress and oxidative stress in ameloblasts. Cell stress induces gene repression, mitochondrial damage and apoptosis. An aromatic fatty acid, 4-phenylbutyrate (4PBA) is a chemical chaperone that interacts with misfolded proteins to prevent ER stress. We hypothesized that 4PBA ameliorates fluoride-induced ER stress in ameloblasts. To determine whether 4PBA protects ameloblasts from fluoride toxicity, we analyzed gene expression of Tgf-β1, Bcl2/Bax ratio and cytochrome-c release in vitro. In vivo, we measured fluorosis levels, enamel hardness and fluoride concentration. Fluoride treated Ameloblast-lineage cells (ALC) had decreased Tgf-β1 expression and this was reversed by 4PBA treatment. The anti-apoptotic Blc2/Bax ratio was significantly increased in ALC cells treated with fluoride/4PBA compared to fluoride treatment alone. Fluoride treatment induced cytochrome-c release from mitochondria into the cytosol and this was inhibited by 4PBA treatment. These results suggest that 4PBA mitigates fluoride-induced gene suppression, apoptosis and mitochondrial damage in vitro. In vivo, C57BL/6J mice were provided fluoridated water for six weeks with either fluoride free control-chow or 4PBA-containing chow (7 g/kg 4PBA). With few exceptions, enamel microhardness, fluorosis levels, and fluoride concentrations of bone and urine did not differ significantly between fluoride treated animals fed with control-chow or 4PBA-chow. Although 4PBA mitigated high-dose fluoride toxicity in vitro, a diet rich in 4PBA did not attenuate dental fluorosis in rodents. Perhaps, not enough intact 4PBA reaches the rodent ameloblasts necessary to reverse the effects of fluoride toxicity. Further studies will be required to optimize protocols for 4PBA administration in vivo in order to evaluate the effect of 4PBA on dental fluorosis. PMID:28553235

4-phenylbutyrate Mitigates Fluoride-Induced Cytotoxicity in ALC Cells.

PubMed

Suzuki, Maiko; Everett, Eric T; Whitford, Gary M; Bartlett, John D

2017-01-01

Chronic fluoride over-exposure during pre-eruptive enamel development can cause dental fluorosis. Severe dental fluorosis is characterized by porous, soft enamel that is vulnerable to erosion and decay. The prevalence of dental fluorosis among the population in the USA, India and China is increasing. Other than avoiding excessive intake, treatments to prevent dental fluorosis remain unknown. We previously reported that high-dose fluoride induces endoplasmic reticulum (ER) stress and oxidative stress in ameloblasts. Cell stress induces gene repression, mitochondrial damage and apoptosis. An aromatic fatty acid, 4-phenylbutyrate (4PBA) is a chemical chaperone that interacts with misfolded proteins to prevent ER stress. We hypothesized that 4PBA ameliorates fluoride-induced ER stress in ameloblasts. To determine whether 4PBA protects ameloblasts from fluoride toxicity, we analyzed gene expression of Tgf -β 1, Bcl2 / Bax ratio and cytochrome-c release in vitro . In vivo , we measured fluorosis levels, enamel hardness and fluoride concentration. Fluoride treated Ameloblast-lineage cells (ALC) had decreased Tgf -β 1 expression and this was reversed by 4PBA treatment. The anti-apoptotic Blc2 / Bax ratio was significantly increased in ALC cells treated with fluoride/4PBA compared to fluoride treatment alone. Fluoride treatment induced cytochrome-c release from mitochondria into the cytosol and this was inhibited by 4PBA treatment. These results suggest that 4PBA mitigates fluoride-induced gene suppression, apoptosis and mitochondrial damage in vitro . In vivo , C57BL/6J mice were provided fluoridated water for six weeks with either fluoride free control-chow or 4PBA-containing chow (7 g/kg 4PBA). With few exceptions, enamel microhardness, fluorosis levels, and fluoride concentrations of bone and urine did not differ significantly between fluoride treated animals fed with control-chow or 4PBA-chow. Although 4PBA mitigated high-dose fluoride toxicity in vitro , a diet rich in 4PBA did not attenuate dental fluorosis in rodents. Perhaps, not enough intact 4PBA reaches the rodent ameloblasts necessary to reverse the effects of fluoride toxicity. Further studies will be required to optimize protocols for 4PBA administration in vivo in order to evaluate the effect of 4PBA on dental fluorosis.

Sirt1 overexpression suppresses fluoride-induced p53 acetylation to alleviate fluoride toxicity in ameloblasts responsible for enamel formation.

PubMed

Suzuki, Maiko; Ikeda, Atsushi; Bartlett, John D

2018-03-01

Low-dose fluoride is an effective caries prophylactic, but high-dose fluoride is an environmental health hazard that causes skeletal and dental fluorosis. Treatments to prevent fluorosis and the molecular pathways responsive to fluoride exposure remain to be elucidated. Previously we showed that fluoride activates SIRT1 as an adaptive response to protect cells. Here, we demonstrate that fluoride induced p53 acetylation (Ac-p53) [Lys379], which is a SIRT1 deacetylation target, in ameloblast-derived LS8 cells in vitro and in enamel organ in vivo. Here we assessed SIRT1 function on fluoride-induced Ac-p53 formation using CRISPR/Cas9-mediated Sirt1 knockout (LS8 Sirt/KO ) cells or CRISPR/dCas9/SAM-mediated Sirt1 overexpressing (LS8 Sirt1/over ) cells. NaF (5 mM) induced Ac-p53 formation and increased cell cycle arrest via Cdkn1a/p21 expression in Wild-type (WT) cells. However, fluoride-induced Ac-p53 was suppressed by the SIRT1 activator resveratrol (50 µM). Without fluoride, Ac-p53 persisted in LS8 Sirt/KO cells, whereas it decreased in LS8 Sirt1/over . Fluoride-induced Ac-p53 formation was also suppressed in LS8 Sirt1/over cells. Compared to WT cells, fluoride-induced Cdkn1a/p21 expression was elevated in LS8 Sirt/KO and these cells were more susceptible to fluoride-induced growth inhibition. In contrast, LS8 Sirt1/over cells were significantly more resistant. In addition, fluoride-induced cytochrome-c release and caspase-3 activation were suppressed in LS8 Sirt1/over cells. Fluoride induced expression of the DNA double strand break marker γH2AX in WT cells and this was augmented in LS8 Sirt1/KO cells, but was attenuated in LS8 Sirt1/over cells. Our results suggest that SIRT1 deacetylates Ac-p53 to mitigate fluoride-induced cell growth inhibition, mitochondrial damage, DNA damage and apoptosis. This is the first report implicating Ac-p53 in fluoride toxicity.

Inducing fluorescence of uranyl acetate as a dual-purpose contrast agent for correlative light-electron microscopy with nanometre precision.

PubMed

Tuijtel, Maarten W; Mulder, Aat A; Posthuma, Clara C; van der Hoeven, Barbara; Koster, Abraham J; Bárcena, Montserrat; Faas, Frank G A; Sharp, Thomas H

2017-09-05

Correlative light-electron microscopy (CLEM) combines the high spatial resolution of transmission electron microscopy (TEM) with the capability of fluorescence light microscopy (FLM) to locate rare or transient cellular events within a large field of view. CLEM is therefore a powerful technique to study cellular processes. Aligning images derived from both imaging modalities is a prerequisite to correlate the two microscopy data sets, and poor alignment can limit interpretability of the data. Here, we describe how uranyl acetate, a commonly-used contrast agent for TEM, can be induced to fluoresce brightly at cryogenic temperatures (-195 °C) and imaged by cryoFLM using standard filter sets. This dual-purpose contrast agent can be used as a general tool for CLEM, whereby the equivalent staining allows direct correlation between fluorescence and TEM images. We demonstrate the potential of this approach by performing multi-colour CLEM of cells containing equine arteritis virus proteins tagged with either green- or red-fluorescent protein, and achieve high-precision localization of virus-induced intracellular membrane modifications. Using uranyl acetate as a dual-purpose contrast agent, we achieve an image alignment precision of ~30 nm, twice as accurate as when using fiducial beads, which will be essential for combining TEM with the evolving field of super-resolution light microscopy.

Distribution of ciprofloxacin into the central nervous system in rats with acute renal or hepatic failure.

PubMed

Naora, K; Ichikawa, N; Hirano, H; Iwamoto, K

1999-05-01

Pharmacokinetic changes of various drugs have been reported in renal or hepatic failure. The present study employed ciprofloxacin, a quinolone antibiotic having neurotoxic side effects, to assess the influence of these diseases on distribution of ciprofloxacin into the central nervous system (CNS). After intravenous dosing of ciprofloxacin (10-30 mg kg(-1)), ciprofloxacin levels in plasma and brain were measured in normal rats (Wistar, male, 10-week-old) and those with acute renal and hepatic injuries which were induced by uranyl nitrate and carbon tetrachloride (CCl4), respectively. In the uranyl nitrate-treated rats, the plasma elimination half-life of ciprofloxacin was prolonged and the total body clearance was reduced when compared with those in the normal rats. Similar but smaller changes were observed in the CCl4-treated group. Brain levels of ciprofloxacin were significantly increased by both uranyl nitrate and CCl4 treatments. A proportional correlation between serum unbound levels and brain levels of ciprofloxacin was observed in the normal group. However, brain-to-serum unbound concentration ratios of ciprofloxacin were reduced in the rats with renal or hepatic failure. These results suggest that renal failure as well as hepatic failure retards elimination of ciprofloxacin from the blood, leading to elevation of the CNS level, and also that ciprofloxacin distribution in the brain is reduced in these disease states.

Coordination trends in alkali metal crown ether uranyl halide complexes: the series [A(crown)]2[UO(2)X(4)] where A=Li, Na, K and X=Cl, Br.

PubMed

Danis, J A; Lin, M R; Scott, B L; Eichhorn, B W; Runde, W H

2001-07-02

UO(2)(C(2)H(3)O(2))(2).2H(2)O reacts with AX or A(C(2)H(3)O(2) or ClO(4)) (where A = Li, Na, K; X = Cl, Br) and crown ethers in HCl or HBr aqueous solutions to give the sandwich-type compounds [K(18-crown-6)](2)[UO(2)Cl(4)] (1), [K(18-crown-6)](2)[UO(2)Br(4)] (2), [Na(15-crown-5)](2)[UO(2)Cl(4)] (3), [Na(15-crown-5)](2)[UO(2)Br(4)] (4), [Li(12-crown-4)](2)[UO(2)Cl(4)] (5), and [Li(12-crown-4)](2)[UO(2)Br(4)] (6). The compounds have been characterized by single-crystal X-ray diffraction, powder diffraction, elemental analysis, IR, and Raman spectroscopy. The [UO(2)X(4)](2-) ions coordinate to two [A(crown)](+) cations through the four halides only (2), through two halides only (3), through the two uranyl oxygens and two halides (3, 4), or through the two uranyl oxygen atoms only (5, 6). Raman spectra reveal nu(U-O) values that correlate with expected trends. The structural trends are discussed within the context of classical principles of hard-soft acid-base theory.

[Chronic combined effects of fluoride and arsenite on the Runx2 and downstream related factors of bone metabolism in rats].

PubMed

Hong, Feng; Zheng, Chong; Xu, De-gan; Qian, Ya-li

2013-09-01

To observe the chronic combined effects of sodium fluoride and sodium arsenite on the Runx2 and downstream related factors of bone metabolism in SD rats. SD rats were divided randomly into nine groups of 6 each by factorial experimental design (half female and half male) , and supplied with the different doses of fluoride, arsenite and fluoride plus arsenite containing in deionized water (untreated control containing 0 mg/kg fluoride and 0 mg/kg arsenite, and low-fluoride and high supplemented with 5 and 20 mg/kg fluoride, and low-arsenite and high supplemented with 2.5 and 10 mg/kg arsenite, and low-fluoride plus low-arsenite, and low-fluoride plus high-arsenite, and high-fluoride plus low-arsenite, and high-fluoride plus high-arsenite, respectively) . After 6 months exposure, the concentration of Runx2, matrix metallopeptidase 9 (MMP-9) ,Osterix, Receptor activator for nuclear factor-κ β ligand (RANKL) were detected by enzyme-linked immunosorbent assay method, respectively. There were no dental fluorosis found in the control group, low-arsenic group and high-arsenic group. There were significant differences in the constituent ratio of dental fluorosis among the rats from low-fluoride and high-fluoride (that is 5 rats out of 6 and 6 rats out of 6) compared with the control group (0 rat out of 6) (χ(2) = 8.57, 12.00, P < 0.05). The bone fluorine level increased with the increase of fluoride dose, the groups without fluoride supply (control group, low-arsenite and high-arsenite group's geometric mean (minimum-maximum) were 0.005 (0.003-0.009), 0.006 (0.003-0.021), 0.003 (0.002-0.100) mg/g, respectively), low-fluorine groups (low-fluoride group, low-fluoride plus low-arsenite, and low-fluoride plus high-arsenite group were 3.395 (2.416-5.871), 3.809 (1.471-7.799), 1.471 (1.473-6.732)mg/g, respectively) , the high-fluorine groups (high-fluoride, high-fluoride plus low-arsenite, and high-fluoride plus high-arsenite group were 70.086 (46.183-131.927), 69.925 (40.503-96.183), 40.503 (52.622-89.487) mg/g, respectively) and the differences between groups was significant (P < 0.05). The bone arsenic level increased with the increase of arsenite dose. The low-arsenic groups (low-arsenite group, low-arsenite plus low-fluoride, and low-arsenite plus high-fluoride group were 7.195 (5.060-9.860), 6.518 (2.960-12.130), 6.970 (3.400-9.730) µg/g, respectively), the high-arsenic groups (high-arsenite, high-arsenite plus low-fluoride, and high-fluoride plus high-arsenite group's geometric mean(minimum-maximum) were 8.823 (5.760-10.840), 9.470 (7.230-12.860), 8.321 (2.420-17.540) µg/g, respectively) were significantly higher than that in the groups without arsenic supply (control group, low-fluoride and high-fluoride group were 1.785 (0.300-3.750), 2.226 (1.410-3.980), 2.030 (1.040-3.850)µg/g, respectively) (P < 0.05). There was no significant difference of the bone arsenic concentration between low-arsenic and high arsenic group. There was significant positive correlation between fluoride concentration and Runx2, MMP-9, Osterix, RANKL level (the correlation coefficient was 0.647, 0.354, 0.582, 0.613 between fluorine gavage concentration and protein level, the correlation coefficient was 0.559,0.387, 0.487, 0.525 between bone fluorine concentration and protein level, respectively, P < 0.01). There was negative correlation between arsenite gavage concentration with Runx2 level (r = -0.527, P < 0.05) and was no correlation between arsenite gavage concentration with MMP-9, RANKL,Osterix level (P > 0.05). There was interaction between fluoride and arsenite to Runx2, MMP-9, RANKL,Osterix (F = 3.88, 15.66, 2.92, 6.42, respectively, P = 0.01, <0.01, 0.031, <0.01, respectively). The combined effects of fluoride and arsenic on the Runx2, MMP-9, RANKL, Osterix of bone metabolism showed antagonistic effects.

Ion release from, and fluoride recharge of a composite with a fluoride-containing bioactive glass.

PubMed

Davis, Harry B; Gwinner, Fernanda; Mitchell, John C; Ferracane, Jack L

2014-10-01

Materials that are capable of releasing ions such as calcium and fluoride, that are necessary for remineralization of dentin and enamel, have been the topic of intensive research for many years. The source of calcium has most often been some form of calcium phosphate, and that for fluoride has been one of several metal fluoride or hexafluorophosphate salts. Fluoride-containing bioactive glass (BAG) prepared by the sol-gel method acts as a single source of both calcium and fluoride ions in aqueous solutions. The objective of this investigation was to determine if BAG, when added to a composite formulation, can be used as a single source for calcium and fluoride ion release over an extended time period, and to determine if the BAG-containing composite can be recharged upon exposure to a solution of 5000ppm fluoride. BAG 61 (61% Si; 31% Ca; 4% P; 3% F; 1% B) and BAG 81 (81% Si; 11% Ca; 4% P; 3% F; 1% B) were synthesized by the sol-gel method. The composite used was composed of 50/50 Bis-GMA/TEGDMA, 0.8% EDMAB, 0.4% CQ, and 0.05% BHT, combined with a mixture of BAG (15%) and strontium glass (85%) to a total filler load of 72% by weight. Disks were prepared, allowed to age for 24h, abraded, then placed into DI water. Calcium and fluoride release was measured by atomic absorption spectroscopy and fluoride ion selective electrode methods, respectively, after 2, 22, and 222h. The composite samples were then soaked for 5min in an aqueous 5000ppm fluoride solution, after which calcium and fluoride release was again measured at 2, 22, and 222h time points. Prior to fluoride recharge, release of fluoride ions was similar for the BAG 61 and BAG 81 composites after 2h, and also similar after 22h. At the four subsequent time points, one prior to, and three following fluoride recharge, the BAG 81 composite released significantly more fluoride ions (p<0.05). Both composites were recharged by exposure to 5000ppm fluoride, although the BAG 81 composite was recharged more than the BAG 61 composite. The BAG 61 composite released substantially more calcium ions prior to fluoride recharge during each of the 2 and 22h time periods. Thereafter, the release of calcium at the four subsequent time points was not significantly different (p>0.05) for the two composites. These results show that, when added to a composite formulation, fluoride-containing bioactive glass made by the sol-gel route can function as a single source for both calcium and fluoride ions, and that the composite can be readily recharged with fluoride. Copyright © 2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Exposure to fluoride in smelter workers in a primary aluminum industry in India.

PubMed

Susheela, A K; Mondal, N K; Singh, A

2013-04-01

Fluoride is used increasingly in a variety of industries in India. Emission of fluoride dust and fumes from the smelters of primary aluminum producing industries is dissipated in the work environment and poses occupational health hazards. To study the prevalence of health complaints and its association with fluoride level in body fluids of smelter workers in a primary aluminum producing industry. In an aluminum industry, health status of 462 smelter workers, 60 supervisors working in the smelter unit, 62 non-smelter workers (control group 1) and 30 administration staff (control group 2) were assessed between 2007 and 2009. Their health complaints were recorded and categorized into 4 groups: 1) gastro-intestinal complaints; 2) non-skeletal manifestations; 3) skeletal symptoms; and (4) respiratory problems. Fluoride level in body fluids, nails, and drinking water was tested by an ion selective electrode; hemoglobin level was tested using HemoCue. The total complaints reported by study groups were significantly higher than the control groups. Smelter workers had a significantly (p<0.001) higher urinary and serum fluoride level than non-smelter workers; the nail fluoride content was also higher in smelter workers than non-smelter workers (p<0.001). The smelter workers with higher hemoglobin level had a significantly (p<0.001) lower urinary fluoride concentration and complained less frequently of health problems. Only 1.4% of the smelter workers were consuming water with high fluoride concentrations. A high percentage of participants was using substances with high fluoride contents. Industrial emission of fluoride is not the only important sources of fluoride exposure--consumption of substance with high levels of fluoride is another important route of entry of fluoride into the body. Measurement of hemoglobin provides a reliable indicator for monitoring the health status of employees at risk of fluorosis.

No calcium-fluoride-like deposits detected in plaque shortly after a sodium fluoride mouthrinse.

PubMed

Vogel, G L; Tenuta, L M A; Schumacher, G E; Chow, L C

2010-01-01

Plaque 'calcium-fluoride-like' (CaF(2)-like) and fluoride deposits held by biological/bacterial calcium fluoride (Ca-F) bonds appear to be the source of cariostatic concentrations of fluoride in plaque fluid. The aim of this study was to quantify the amounts of plaque fluoride held in these reservoirs after a sodium fluoride rinse. 30 and 60 min after a 228 microg/g fluoride rinse, plaque samples were collected from 11 volunteers. Each sample was homogenized, split into 2 aliquots (aliquots 1 and 2), centrifuged, and the recovered plaque fluid combined and analyzed using microelectrodes. The plaque mass from aliquot 1 was retained. The plaque mass from aliquot 2 was extracted several times with a solution having the same fluoride, calcium and pH as the plaque fluid in order to extract the plaque CaF(2)-like deposits. The total fluoride in both aliquots was then determined. In a second experiment, the extraction completeness was examined by applying the above procedure to in vitro precipitates containing known amounts of CaF(2)-like deposits. Nearly identical fluoride concentrations were found in both plaque aliquots. The extraction of the CaF(2)-like precipitates formed in vitro removed more than 80% of these deposits. The results suggest that either CaF(2)-like deposits were not formed in plaque or, if these deposits had been formed, they were rapidly lost. The inability to form persistent amounts of CaF(2)-like deposits in plaque may account for the relatively rapid loss of plaque fluid fluoride after the use of conventional fluoride dentifrices or rinses. (c) 2010 S. Karger AG, Basel.

Child-education program for the reduction of health risks due to fluoride in water sources in the Chiang Mai Basin, Thailand.

PubMed

Takizawa, S; Takeda, T; Wongrueng, A; Wattanachira, S

2010-01-01

Groundwater is the major source of drinking water in Lamphun Province in the Chiang Mai Basin, Thailand. However, groundwater contains high fluoride up to 16 mg F/L, which has caused dental and skeletal fluorosis. Although Thai Government installed RO membrane plants for the removal of fluoride from groundwater; and delivers RO-filtered bottled water that contains less fluoride than the Thai Standard of 0.7 mg F/L, it was found that the urinary fluoride levels are still high among the residents. To find the major sources of fluoride intake, fluoride contents in various water sources, such as village water supply, shallow and deep groundwaters, rain water and bottled water, were measured, and the local people's behavior on water uses was recorded by interview and questionnaire study. As a result, it was found that the highest risk of fluoride ingestion comes from cooking rice with fluoride-containing water because of a lack of knowledge on fluoride sources and fluoride chemistry. To reduce the health risks arising from fluoride intake, a hands-on educational program on the sources and risks of fluoride in water was developed and implemented in the local schools. The participatory educational program promoted active involvement of schoolchildren, but it was found that the effectiveness of education varied depending on the questions we asked. Therefore, it needs to be improved by an iterative and interactive educational program. In conclusion, it was found that the benefits of providing safe drinking water using such advanced technology as RO membrane can be maximized only when it comes along with a participatory educational program on fluoride sources and health risks.

A study to investigate fluoride contamination and fluoride exposure dose assessment in lateritic zones of West Bengal, India.

PubMed

Samal, Alok C; Bhattacharya, Piyal; Mallick, Anusaya; Ali, Md Motakabber; Pyne, Jagadish; Santra, Subhas C

2015-04-01

To assess the status of severity of fluoride contamination in lateritic Bankura and Purulia districts of West Bengal, concentrations of fluoride in different water sources and agricultural field soils were investigated. The fluoride content (mg/l) was observed to differ with aquifer depths: 0.19-0.47 in dug wells, 0.01-0.17 in shallow tube wells, and 0.07-1.6 in deep tube wells. Fluoride within the World Health Organization (WHO) prescribed range (1.0-1.5 mg/l) was estimated only in ~17% of the total collected water samples while ~67% showed <0.7 mg/l fluoride and thus may impede in the production and maintenance of healthy teeth and bones of the residents, especially children. Fluoride in water was found to be significantly correlated (r = 0.63) with pH. The exposure dose of fluoride (mg/kg/day) from drinking water in infants, children, and adults was estimated in the ranges 0.02-0.53, 0.01-0.24, and 0.01-0.14, respectively against the standard value of 0.05. A clear risk of dental fluorosis is apparent in infants and children of the study area. The fluoride in soil (55-399 mg/kg) was detected to be significantly correlated with the fluoride content in deep tube wells and soil pH (r = 0.56 and 0.71, respectively). The relationships of soil fluoride with total hardness and that with phosphate were not significant. There is a high possibility of bioaccumulation of fluoride from contaminated soil and water of the study area to cultivated crops. This will enhance the quantity of fluoride intake into human food chain in addition to drinking water pathway.

Effect of water fluoridation on the development of medial vascular calcification in uremic rats.

PubMed

Martín-Pardillos, Ana; Sosa, Cecilia; Millán, Ángel; Sorribas, Víctor

2014-04-06

Public water fluoridation is a common policy for improving dental health. Fluoride replaces the hydroxyls of hydroxyapatite, thereby improving the strength of tooth enamel, but this process can also occur in other active calcifications. This paper studies the effects of water fluoridation during the course of vascular calcification in renal disease. The effect of fluoride was studied in vitro and in vivo. Rat aortic smooth muscle cells were calcified with 2mM Pi for 5 days. Fluoride concentrations of 5-10 μM--similar to those found in people who drink fluoridated water--partially prevented calcification, death, and osteogene expression in vitro. The anticalcifying mechanism was independent of cell activity, matrix Gla protein, and fetuin A expressions, and it exhibited an IC50 of 8.7 μM fluoride. In vivo, however, fluoridation of drinking water at 1.5mg/L (concentration recommended by the WHO) and 15 mg/L dramatically increased the incipient aortic calcification observed in rats with experimental chronic kidney disease (CKD, 5/6-nephrectomy), fed a Pi-rich fodder (1.2% Pi). Fluoride further declined the remaining renal function of the CKD animals, an effect that most likely overwhelmed the positive effect of fluoride on calcification in vitro. Ultrastructural analysis revealed that fluoride did not modify the Ca/P atomic ratio, but it was incorporated into the lattice of in vivo deposits. Fluoride also converted the crystallization pattern from plate to rode-like structures. In conclusion, while fluoride prevents calcification in vitro, the WHO's recommended concentrations in drinking water become nephrotoxic to CKD rats, thereby aggravating renal disease and making media vascular calcification significant. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Fluoride exposure and indicators of thyroid functioning in the Canadian population: implications for community water fluoridation.

PubMed

Barberio, Amanda M; Hosein, F Shaun; Quiñonez, Carlos; McLaren, Lindsay

2017-10-01

There are concerns that altered thyroid functioning could be the result of ingesting too much fluoride. Community water fluoridation (CWF) is an important source of fluoride exposure. Our objectives were to examine the association between fluoride exposure and (1) diagnosis of a thyroid condition and (2) indicators of thyroid functioning among a national population-based sample of Canadians. We analysed data from Cycles 2 and 3 of the Canadian Health Measures Survey (CHMS). Logistic regression was used to assess associations between fluoride from urine and tap water samples and the diagnosis of a thyroid condition. Multinomial logistic regression was used to examine the relationship between fluoride exposure and thyroid-stimulating hormone (TSH) level (low/normal/high). Other available variables permitted additional exploratory analyses among the subset of participants for whom we could discern some fluoride exposure from drinking water and/or dental products. There was no evidence of a relationship between fluoride exposure (from urine and tap water) and the diagnosis of a thyroid condition. There was no statistically significant association between fluoride exposure and abnormal (low or high) TSH levels relative to normal TSH levels. Rerunning the models with the sample constrained to the subset of participants for whom we could discern some source(s) of fluoride exposure from drinking water and/or dental products revealed no significant associations. These analyses suggest that, at the population level, fluoride exposure is not associated with impaired thyroid functioning in a time and place where multiple sources of fluoride exposure, including CWF, exist. © Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2017. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

No Calcium-Fluoride-Like Deposits Detected in Plaque Shortly after a Sodium Fluoride Mouthrinse

PubMed Central

Vogel, G.L.; Tenuta, L.M.A.; Schumacher, G.E.; Chow, L.C.

2010-01-01

Plaque ‘calcium-fluoride-like’ (CaF2-like) and fluoride deposits held by biological/bacterial calcium fluoride (Ca-F) bonds appear to be the source of cariostatic concentrations of fluoride in plaque fluid. The aim of this study was to quantify the amounts of plaque fluoride held in these reservoirs after a sodium fluoride rinse. 30 and 60 min after a 228 μg/g fluoride rinse, plaque samples were collected from 11 volunteers. Each sample was homogenized, split into 2 aliquots (aliquots 1 and 2), centrifuged, and the recovered plaque fluid combined and analyzed using microelectrodes. The plaque mass from aliquot 1 was retained. The plaque mass from aliquot 2 was extracted several times with a solution having the same fluoride, calcium and pH as the plaque fluid in order to extract the plaque CaF2-like deposits. The total fluoride in both aliquots was then determined. In a second experiment, the extraction completeness was examined by applying the above procedure to in vitro precipitates containing known amounts of CaF2-like deposits. Nearly identical fluoride concentrations were found in both plaque aliquots. The extraction of the CaF2-like precipitates formed in vitro removed more than 80% of these deposits. The results suggest that either CaF2-like deposits were not formed in plaque or, if these deposits had been formed, they were rapidly lost. The inability to form persistent amounts of CaF2-like deposits in plaque may account for the relatively rapid loss of plaque fluid fluoride after the use of conventional fluoride dentifrices or rinses. PMID:20185917

Validation of a Cariogenic Biofilm Model to Evaluate the Effect of Fluoride on Enamel and Root Dentine Demineralization.

PubMed

Fernández, Constanza E; Tenuta, Livia M A; Cury, Jaime A

2016-01-01

Due to gingival recession both enamel and root dentine are at risk of developing caries. Both tissues are exposed to a similar environment, however there is not a validated model to evaluate the effect of fluoride on these dental substrates simultaneously. Hence, this study aimed to validate a caries model to evaluate the effect of fluoride to prevent demineralization on enamel and root-dentine. Streptococcus mutans UA159 biofilms were formed on saliva-coated bovine enamel and root dentine slabs (n = 12 per group) mounted in the same well of culture plates. The biofilms were exposed 8×/day to 10% sucrose and treated 2×/day with fluoridated solutions containing 0, 150, 450, or 1,350 ppm F; thus, simulating the use of low to high fluoride concentration toothpastes. The pH values of the culture medium was monitored 2×/day as a biofilm acidogenicity indicator. After 96 h, biofilms were collected for fluoride concentration analysis. The percentage of surface hardness loss (%SHL) was calculated for slabs. The fluoride uptake by the enamel and dentine was also determined. The model showed a dose-response because the biofilm and fluoride uptake increased and %SHL decreased at increasing fluoride concentrations (p < 0.05). Fluoride in the biofilm formed on dentine and fluoride uptake by dentine were higher than those for enamel. With the same fluoride concentration treatment, the percentage of reduction of demineralization was lower for dentine than for enamel. In conclusion, the model was validated in terms of a dose-response effect of fluoride on enamel and root dentine. Furthermore, the findings support the clinical data, suggesting that higher fluoride concentrations are necessary to control caries of root dentine than of enamel.

Effects of fluoride emissions on enzyme activity in metabolism of agricultural plants

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

Moeri, P.B.

1980-01-01

The effects of fluoride on the activity of malatedehydrogenase (MDH) in rape seed and rye grass have been investigated. Fluoride, which has been absorbed from the air, seems to act differently from fluoride added to the soil. The action of airborne fluoride compounds resorbed by the plant on the activity of MDH significantly correlated with the distance from an aluminum plant, crop yield, and fluoride content. 5 references, 5 figures, 2 tables.

Chemical Ignition of Flame Throwers

DTIC Science & Technology

1944-04-20

fluorinating agents such as fluorine, antimony penta- fluoride, oxygen fluoride or bromine and chlorine trifluoride mixtures be evaluated. The use...0F2), and bromine and chlorine trifluoride mixtures (BrF3-ClF3). Oxygen fluoride, a gas boiling at -l67°C., has the interesting property of being...ShFc), oxygen fluoride (0F2), and bromine and chlorine fluoride mixtures (BrF3-ClFsJ. Oxygen fluoride Is stable In the presence of moisture. 4

Water fluoridation and dental caries in 5- and 12-year-old children from Canterbury and Wellington.

PubMed

Lee, Martin; Dennison, Peter J

2004-03-01

Claims have been made that the effectiveness of water fluoridation has reduced due to the widespread availability of other sources of fluoride. This study examines the differences in the oral health of children living in fluoridated and non-fluoridated areas of Canterbury and Wellington, New Zealand. The data used in this cross-sectional study had been routinely collected into a computerized data-collection system by the School Dental Services in the two study areas. Records of dental status (dmfs/DMFS), fluoridation status, ethnicity, and socio-economic status for 8030 5-year-olds, and 6916 12-year-olds in 1996 were analysed. Caries prevalence and severity was consistently lower for children in the fluoridated area for both age groups, and within all subgroups. Five-year-olds in the fluoridated area had 2.63 dmfs (sd, 5.88), and those in the non-fluoridated area 3.80 dmfs (sd, 6.79). For 12-year-olds the respective figures were 1.39 DMFS (sd, 2.30) and 2.37 DMFS (sd, 3.46). Multivariable analysis confirmed the independent association between water fluoridation and better dental health. This results of this study show children living in a fluoridated area to have significantly better oral health compared to those not in a fluoridated area. These differences are greater for Maori and Pacific children and children of low socio-economic status.

Fluoride Exposure Aggravates the Testicular Damage and Sperm Quality in Diabetic Mice: Protective Role of Ginseng and Banaba.

PubMed

Sm, Saumya; Mahaboob Basha, P

2017-06-01

Fluoride toxicity is known to pose infertility in fluoride-intoxicated animals as well as in people residing in fluoride endemic zones. The present study addresses the degree of impairments caused due to co-exposure of high fluoride toxicity in diabetic mice. Swiss mice, Mus musculus, were subjected to fluoride toxicity by providing fluoride-supplemented drinking water (600 ppm NaF) for a period of 30 days after the confirmation of streptozotocin-induced diabetes(STZ, 50 mg/kgbw). Consequently, aggravated hyperglycemia and tissue fluoride accumulation were witnessed in fluoride-intoxicated diabetic mice; later, these toxicated mice were treated with ginseng extract (GE) and banaba leaf extract, (BLE) at dose of 150 mg/kgbw/day alone and in combination for 15 and 30-day duration to check the efficacy of phytoextracts in reversing the toxicity. The spermatological indices studied, such as sperm density, motility, viability and morphology as well as the testicular biochemical parameters showed enhanced impairment in reproductive status of fluoride-intoxicated diabetic mice. Further, 15-days administration of GE and BLE in combination at a dose of 150 mg/kgbw/day was found to be beneficial in normalizing the alterations observed upon fluoride intoxication to diabetic mice. However, the correlates showed moderate association between blood glucose levels and the spermatological as well as biochemical indices wherein the tissue fluoride levels correlate least.

Analysis of differentially expressed genes between fluoride-sensitive and fluoride-endurable individuals in midgut of silkworm, Bombyx mori.

PubMed

Qian, Heying; Li, Gang; He, Qingling; Zhang, Huaguang; Xu, Anying

2016-08-15

Fluoride tolerance is an economically important trait of silkworm. Near-isogenic lines (NILs) of the dominant endurance to fluoride (Def) gene in Bombyx mori has been constructed before. Here, we analyzed the gene expression profiles of midgut of fluoride-sensitive and fluoride-endurable individuals of Def NILs by using high-throughput Illumina sequencing technology and bioinformatics tools, and identified differentially expressed genes between these individuals. A total of 3,612,399 and 3,567,631 clean tags for the libraries of fluoride-endurable and fluoride-sensitive individuals were obtained, which corresponded to 32,933 and 43,976 distinct clean tags, respectively. Analysis of differentially expressed genes indicates that 241 genes are differentially expressed between the two libraries. Among the 241 genes, 30 are up-regulated and 211 are down-regulated in fluoride-endurable individuals. Pathway enrichment analysis demonstrates that genes related to ribosomes, pancreatic secretion, steroid biosynthesis, glutathione metabolism, steroid biosynthesis, and glycerolipid metabolism are down-regulated in fluoride-endurable individuals. qRT-PCR was conducted to confirm the results of the DGE. The present study analyzed differential expression of related genes and tried to find out whether the crucial genes were related to fluoride detoxification which might elucidate fluoride effect and provide a new way in the fluorosis research. Copyright © 2016 Elsevier B.V. All rights reserved.

Ameliorative effects of oleanolic acid on fluoride induced metabolic and oxidative dysfunctions in rat brain: Experimental and biochemical studies.

PubMed

Sarkar, Chaitali; Pal, Sudipta; Das, Niranjan; Dinda, Biswanath

2014-04-01

Beneficial effects of oleanolic acid on fluoride-induced oxidative stress and certain metabolic dysfunctions were studied in four regions of rat brain. Male Wistar rats were treated with sodium fluoride at a dose of 20 mg/kg b.w./day (orally) for 30 days. Results indicate marked reduction in acidic, basic and neutral protein contents due to fluoride toxicity in cerebrum, cerebellum, pons and medulla. DNA, RNA contents significantly decreased in those regions after fluoride exposure. Activities of proteolytic enzymes (such as cathepsin, trypsin and pronase) were inhibited by fluoride, whereas transaminase enzyme (GOT and GPT) activities increased significantly in brain tissue. Fluoride appreciably elevated brain malondialdehyde level, free amino acid nitrogen, NO content and free OH radical generation. Additionally, fluoride perturbed GSH content and markedly reduced SOD, GPx, GR and CAT activities in brain tissues. Oral supplementation of oleanolic acid (a plant triterpenoid), at a dose of 5mg/kgb.w./day for last 14 days of fluoride treatment appreciably ameliorated fluoride-induced alteration of brain metabolic functions. Appreciable counteractive effects of oleanolic acid against fluoride-induced changes in protein and nucleic acid contents, proteolytic enzyme activities and other oxidative stress parameters indicate that oleanolic acid has potential antioxidative effects against fluoride-induced oxidative brain damage. Copyright © 2014 Elsevier Ltd. All rights reserved.

Risk Assessment of Fluoride Intake from Tea in the Republic of Ireland and its Implications for Public Health and Water Fluoridation

PubMed Central

Waugh, Declan T.; Potter, William; Limeback, Hardy; Godfrey, Michael

2016-01-01

The Republic of Ireland (RoI) is the only European Country with a mandatory national legislation requiring artificial fluoridation of drinking water and has the highest per capita consumption of black tea in the world. Tea is a hyperaccumulator of fluoride and chronic fluoride intake is associated with multiple negative health outcomes. In this study, fifty four brands of the commercially available black tea bag products were purchased and the fluoride level in tea infusions tested by an ion-selective electrode method. The fluoride content in all brands tested ranged from 1.6 to 6.1 mg/L, with a mean value of 3.3 mg/L. According to our risk assessment it is evident that the general population in the RoI is at a high risk of chronic fluoride exposure and associated adverse health effects based on established reference values. We conclude that the culture of habitual tea drinking in the RoI indicates that the total cumulative dietary fluoride intake in the general population could readily exceed the levels known to cause chronic fluoride intoxication. Evidence suggests that excessive fluoride intake may be contributing to a wide range of adverse health effects. Therefore from a public health perspective, it would seem prudent and sensible that risk reduction measures be implemented to reduce the total body burden of fluoride in the population. PMID:26927146

Risk Assessment of Fluoride Intake from Tea in the Republic of Ireland and its Implications for Public Health and Water Fluoridation.

PubMed

Waugh, Declan T; Potter, William; Limeback, Hardy; Godfrey, Michael

2016-02-26

The Republic of Ireland (RoI) is the only European Country with a mandatory national legislation requiring artificial fluoridation of drinking water and has the highest per capita consumption of black tea in the world. Tea is a hyperaccumulator of fluoride and chronic fluoride intake is associated with multiple negative health outcomes. In this study, fifty four brands of the commercially available black tea bag products were purchased and the fluoride level in tea infusions tested by an ion-selective electrode method. The fluoride content in all brands tested ranged from 1.6 to 6.1 mg/L, with a mean value of 3.3 mg/L. According to our risk assessment it is evident that the general population in the RoI is at a high risk of chronic fluoride exposure and associated adverse health effects based on established reference values. We conclude that the culture of habitual tea drinking in the RoI indicates that the total cumulative dietary fluoride intake in the general population could readily exceed the levels known to cause chronic fluoride intoxication. Evidence suggests that excessive fluoride intake may be contributing to a wide range of adverse health effects. Therefore from a public health perspective, it would seem prudent and sensible that risk reduction measures be implemented to reduce the total body burden of fluoride in the population.

Dental caries and dental fluorosis at varying water fluoride concentrations.

PubMed

Heller, K E; Eklund, S A; Burt, B A

1997-01-01

The purpose of this study was to investigate the relationships between caries experience and dental fluorosis at different fluoride concentrations in drinking water. The impact of other fluoride products also was assessed. This study used data from the 1986-87 National Survey of US School-children. Fluoride levels of school water were used as an indicator of the children's water fluoride exposure. The use of fluoride drops, tablets, professional fluoride treatments, and school fluoride rinses were ascertained from caregiver questionnaires. Only children with a single continuous residence (n = 18,755) were included in this analysis. The sharpest declines in dfs and DMFS were associated with increases in water fluoride levels between 0 and 0.7 ppm F, with little additional decline between 0.7 and 1.2 ppm F. Fluorosis prevalence was 13.5 percent, 21.7 percent, 29.9 percent, and 41.4 percent for children who consumed < 0.3, 0.3 to < 0.7, 0.7 to 1.2, and > 1.2 ppm F water. In addition to fluoridated water, the use of fluoride supplements was associated with both lower caries and increased fluorosis. A suitable trade-off between caries and fluorosis appears to occur around 0.7 ppm F. Data from this study suggest that a reconsideration of the policies concerning the most appropriate concentrations for water fluoridation might be appropriate for the United States.

Association of vascular fluoride uptake with vascular calcification and coronary artery disease.

PubMed

Li, Yuxin; Berenji, Gholam R; Shaba, Wisam F; Tafti, Bashir; Yevdayev, Ella; Dadparvar, Simin

2012-01-01

The feasibility of a fluoride positron emission tomography/computed tomography (PET/CT) scan for imaging atherosclerosis has not been well documented. The purpose of this study was to assess fluoride uptake of vascular calcification in various major arteries, including coronary arteries. We retrospectively reviewed the imaging data and cardiovascular history of 61 patients who received whole-body sodium [¹⁸F]fluoride PET/CT studies at our institution from 2009 to 2010. Fluoride uptake and calcification in major arteries, including coronary arteries, were analyzed by both visual assessment and standardized uptake value measurement. Fluoride uptake in vascular walls was demonstrated in 361 sites of 54 (96%) patients, whereas calcification was observed in 317 sites of 49 (88%) patients. Significant correlation between fluoride uptake and calcification was observed in most of the arterial walls, except in those of the abdominal aorta. Fluoride uptake in coronary arteries was demonstrated in 28 (46%) patients and coronary calcifications were observed in 34 (56%) patients. There was significant correlation between history of cardiovascular events and presence of fluoride uptake in coronary arteries. The coronary fluoride uptake value in patients with cardiovascular events was significantly higher than in patients without cardiovascular events. sodium [¹⁸F]fluoride PET/CT might be useful in the evaluation of the atherosclerotic process in major arteries, including coronary arteries. An increased fluoride uptake in coronary arteries may be associated with an increased cardiovascular risk.

Water fluoridation and osteoporotic fracture.

PubMed

Hillier, S; Inskip, H; Coggon, D; Cooper, C

1996-09-01

Osteoporotic fractures constitute a major public health problem. These fractures typically occur at the hip, spine and distal forearm. Their pathogenesis is heterogeneous, with contributions from both bone strength and trauma. Water fluoridation has been widely proposed for its dental health benefits, but concerns have been raised about the balance of skeletal risks and benefits of this measure. Fluoride has potent effects on bone cell function, bone structure and bone strength. These effects are mediated by the incorporation of fluoride ions in bone crystals to form fluoroapatite, and through an increase in osteoblast activity. It is believed that a minimum serum fluoride level of 100 ng/ml must be achieved before osteoblasts will be stimulated. Serum levels associated with drinking water fluoridated to 1 ppm are usually several times lower than this value, but may reach this threshold at concentrations of 4 ppm in the drinking water. Animal studies suggest no effect of low-level (0-3 ppm) fluoride intake on bone strength, but a possible decrease at higher levels. Sodium fluoride has been used to treat established osteoporosis for nearly 30 years. Recent trials of this agent, prescribed at high doses, have suggested that despite a marked increase in bone mineral density, there is no concomitant reduction in vertebral fracture incidence. Furthermore, the increase in bone density at the lumbar spine may be achieved at the expense of bone mineral in the peripheral cortical skeleton. As a consequence, high dose sodium fluoride (80 mg daily) is not currently used to treat osteoporosis. At lower doses, recent trials have suggested a beneficial effect on both bone density and fracture. The majority of epidemiological evidence regarding the effect of fluoridated drinking water on hip fracture incidence is based on ecological comparisons. Although one Finnish study suggested that hip fracture rates in a town with fluoridated water were lower than those in a matching town without fluoride, a later study failed to show differences. Ecological studies from the United States and Great Britain have, if anything, revealed a weak positive association between water fluoride concentration and hip fracture incidence. Two studies examining hip fracture rates before and after fluoridation yielded discordant results, and are complicated by underlying time trends in hip fracture incidence. Only two studies have attempted to examine the relation between water fluoride concentration and fracture risk at an individual level. In one of these, women in a high fluoride community had double the fracture risk of women in a low fluoride community. In the other, there was no relationship between years of fluoride exposure and incidence of spine or non-spine fractures. In conclusion, the epidemiological evidence relating water fluoridation to hip fracture is based upon ecological comparisons and is inconclusive. However, several studies suggest the possibility of a weak adverse effect, which warrants further exploration. Data on the relationship between fluoride intake and hip fracture risk at the individual level, and data relating fluoridation to bone mineral density are required. Until these become available, the burden of evidence suggesting that fluoridation might be a risk factor for hip fracture is weak and not sufficient to retard the progress of the water fluoridation programme.

21 CFR 175.270 - Poly(vinyl fluoride) resins.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Poly(vinyl fluoride) resins. 175.270 Section 175... Substances for Use as Components of Coatings § 175.270 Poly(vinyl fluoride) resins. Poly(vinyl fluoride... the purpose of this section, poly(vinyl fluoride) resins consist of basic resins produced by the...

21 CFR 175.270 - Poly(vinyl fluoride) resins.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Poly(vinyl fluoride) resins. 175.270 Section 175... Substances for Use as Components of Coatings § 175.270 Poly(vinyl fluoride) resins. Poly(vinyl fluoride... the purpose of this section, poly(vinyl fluoride) resins consist of basic resins produced by the...

[Study on the relationship between renal apoptosis and expression of caspase protein in fluoride induced rat].

PubMed

Gao, Jiping; Song, Guohua; Liu, Maolin; Wang, Yu; Yang, Xia

2014-01-01

To study the relationship between death receptor pathway, mitochondrion pathway and fluoride-induced apoptosis of renal cell. Male Sprague-Dawley rats were divided randomly into four groups (control, low-fluoride, medium-fluoride,and high-fluoride) and administered 0, 50, 100, and 200 mg/L of sodium fluoride, respectively, via drinking water for 120 days. The incidence of dental fluorosis were observed, the body weights and urine fluoride levels were measured. Apoptosis was detected by the Flow Cytometry (FCM). The expressions of protein of Caspase-3, Caspase-8, Caspase-9, Cyt C were detectedby immunohistoehemistry. The apoptosis rate in the fluoride exposed low does group,middle dose group and high dose group increased significantly as compared with control group. The average optical density value of Caspase-3, Caspase-8, Caspase-9 and Cyt C were higher in the fluoride exposed middle dose group and high dose group than those in the control group (P < 0.05). Death receptor pathway and mitochondrion pathway may participate in the process of fluoride-induced apoptosis of renal cell.

Histopathological changes of renal tissue following sodium fluoride administration in two consecutive generations of mice. Correlation with the urinary elimination of fluoride.

PubMed

Dimcevici Poesina, Nicoleta; Bălălău, Cristian; Nimigean, Vanda Roxana; Nimigean, Victor; Ion, Ion; Baconi, Daniela; Bârcă, Maria; Băran Poesina, Violeta

2014-01-01

The present study was designed to investigate the toxic effects (evaluated as histopathological changes) of sodium fluoride on the kidney in two consecutive generations of NMRI mice. An attempt to correlate the toxicity with the urinary elimination of fluoride has been made, as urinary fluoride excretion has been widely used as an indicator of fluoride intake and exposure. Six mixed (males and females) animal groups have been constituted by dividing the populations of mice derived from pregnant females (named "mothers" 0.5 mg sodium fluoride) treated with 0.5 mg sodium fluoride by daily gavage and pregnant females (named "mothers" 0.25 mg sodium fluoride) treated with 0.25 mg sodium fluoride by daily gavage; three types of sodium fluoride treatments were administrated: homeopathic, allopathic-homeopathic and allopathic. When the animals reached the adulthood, by randomization, they were selected in pairs for giving birth to the second generation of mice. No treatments were administrated to the second generation of mice; thus, the urinary elimination of fluoride in the second generation is attributed to exposure at sodium fluoride before birth. The administration of sodium fluoride to the first generation (F1) is realized until the mice reached the adulthood. For the first generation, the urine was collected at three times, every three weeks: at the age of four weeks, seven weeks and 11 weeks; single sampling urine, at the age of four weeks, has been conducted for the second generation. The urine samples have been analyzed using the ion selective electrode method for fluoride. For the histopathological examination, the animals were killed by cervical dislocation; the kidneys were collected in a 10% formalin solution. The preparation of samples for optical microscopy was realized with Hematoxylin-Eosin staining. The results indicate that the elimination of fluoride was similar (at the second evaluation, at 7-week-old of the first generation) for the both generations of mice. Histopathological observation of the kidney has revealed granular dystrophy of the renal tubules, necrosis of the endothelial cells and of the mesangial cells of renal glomerulus. The study indicates that different sodium fluoride treatments produce some pathological aspects of the kidneys and influence the urinary elimination of fluoride in two consecutive generations of mice. For the higher doses, the pathological changes of the kidney are more important, and the urinary elimination of fluoride is higher, especially for the allopathic doses.

Small molecule fluoride toxicity agonists.

PubMed

Nelson, James W; Plummer, Mark S; Blount, Kenneth F; Ames, Tyler D; Breaker, Ronald R

2015-04-23

Fluoride is a ubiquitous anion that inhibits a wide variety of metabolic processes. Here, we report the identification of a series of compounds that enhance fluoride toxicity in Escherichia coli and Streptococcus mutans. These molecules were isolated by using a high-throughput screen (HTS) for compounds that increase intracellular fluoride levels as determined via a fluoride riboswitch reporter fusion construct. A series of derivatives were synthesized to examine structure-activity relationships, leading to the identification of compounds with improved activity. Thus, we demonstrate that small molecule fluoride toxicity agonists can be identified by HTS from existing chemical libraries by exploiting a natural fluoride riboswitch. In addition, our findings suggest that some molecules might be further optimized to function as binary antibacterial agents when combined with fluoride. Copyright © 2015 Elsevier Ltd. All rights reserved.

New insight on the response of bacteria to fluoride.

PubMed

Breaker, R R

2012-01-01

Fluoride has been used for decades to prevent caries and it is well established that this anion can inhibit the growth of bacteria. However, the precise effects that fluoride has on bacteria and the mechanisms that bacteria use to overcome fluoride toxicity have largely remained unexplored. Recently, my laboratory reported the discovery of biological systems that bacteria use to sense fluoride and reduce fluoride toxicity. These sensors and their associated genes are very widespread in biology, which has implications for a number of issues that are central to the use of fluoride for dental care. Below I provide a summary of our findings, comment on some of the key prospects for expanding our understanding of fluoride's effects on biology, and propose some future uses of this knowledge. Copyright © 2012 S. Karger AG, Basel.

New Insight on the Response of Bacteria to Fluoride

PubMed Central

Breaker, R.R.

2012-01-01

Fluoride has been used for decades to prevent caries and it is well established that this anion can inhibit the growth of bacteria. However, the precise effects that fluoride has on bacteria and the mechanisms that bacteria use to overcome fluoride toxicity have largely remained unexplored. Recently, my laboratory reported the discovery of biological systems that bacteria use to sense fluoride and reduce fluoride toxicity. These sensors and their associated genes are very widespread in biology, which has implications for a number of issues that are central to the use of fluoride for dental care. Below I provide a summary of our findings, comment on some of the key prospects for expanding our understanding of fluoride's effects on biology, and propose some future uses of this knowledge. PMID:22327376

Dental Fluorosis and Dental Caries Prevalence among 12 and 15-Year-Old School Children in Nalgonda District, Andhra Pradesh, India.

PubMed

Sukhabogi, J R; Parthasarathi, P; Anjum, S; Shekar, Brc; Padma, Cm; Rani, As

2014-09-01

Fluoride is a double edged sword. The assessment of dental caries and fluorosis in endemic fluoride areas will facilitate in assessing the relation between fluoride concentrations in water with dental caries, dental fluorosis simultaneously. The objective of the following study is to assess the dental caries and dental fluorosis prevalence among 12 and 15-year-old school children in Nalgonda district, Andhra Pradesh, India. This was a cross-sectional study. Two stage cluster sampling technique was employed to select 20 schools from Nalgonda district. The oral examination of available 12 and 15-year-old children fulfilling the inclusion and exclusion criteria was carried out to assess dental caries and fluorosis. The examination was conducted by a single trained and calibrated examiner using the mouth mirror and community periodontal index probe under natural daylight. These areas were divided into four categories, low, medium, high and very high fluoride areas based on the fluoride concentration at the time of statistical analysis. The data was analyzed using Statistical Package for the Social Sciences version 16 (IBM, Chicago, USA). The caries prevalence was less among 12-year-old children (39.9% [369/924]) compared with 15-years-old children (46.7% [444/951]). The prevalence was more among females (50.4% [492/977]) than males (35.8% [321/898]). The prevalence was more in low fluoride area (60.5% [300/496]) followed by very high fluoride area (54.8% [201/367]), high fluoride area (32.4% [293/904]) and medium fluoride area (17.6% [19/108]) in the descending order. The fluorosis prevalence increased with increasing fluoride concentration with no difference in gender and age distribution. Low fluoride areas require fluoridation or alternate sources of fluoride, whereas high fluoride areas require defluoridation. Defluoridation of water is an immediate requirement in areas with fluoride concentration of 4 parts per million and above as dental fluorosis is a public health problem in these areas with 100% prevalence.

Tooth quality in dental fluorosis genetic and environmental factors.

PubMed

Vieira, A P G F; Hanocock, R; Eggertsson, H; Everett, E T; Grynpas, M D

2005-01-01

Dental fluorosis (DF) affects the appearance and structure of tooth enamel and can occur following ingestion of excess fluoride during critical periods of amelogenesis. This tooth malformation may, depending on its severity, influence enamel and dentin microhardness and dentin mineralization. Poor correlation between tooth fluoride (F) concentration and DF severity was shown in some studies, but even when a correlation was present, tooth fluoride concentration explained very little of DF severity. This fact calls into question the generally accepted hypothesis that the main factor responsible for DF severity is tooth fluoride concentration. It has been shown previously that genetic factors (susceptibility to DF) play an important role in DF severity although DF severity relates to individual susceptibility to fluoride exposure (genetics), tooth fluoride concentration relates to fluoride ingestion (environmental). The objective of this study was to investigate the correlation between tooth fluoride concentration, DF severity, and tooth mechanical and materials properties. Three strains of mice (previously shown to have different susceptibility to DF) at weaning were treated with four different levels of F in their water (0, 25, 50, and 100 ppm) for 6 weeks. Mice teeth were tested for fluoride by instrumental neutron activation analysis (INAA), DF severity determined by quantitative light-induced fluorescence [QLF], and tooth quality (enamel and dentin microhardness and dentin mineralization). Tooth fluoride concentration (environment factor) correlated positively with DF severity (QLF) (rs=0.608), fluoride treatment group (rs=0.952). However, tooth fluoride concentration correlated negatively with enamel microhardness (rs=-0.587), dentin microhardness (rs=-0.268) and dentin mineralization (rs=-0.245). Dental fluorosis (genetic factor) severity (QLF) correlated positively with fluoride treatment (rs=0.608) and tooth fluoride concentration (rs=0.583). DF severity correlated negatively with enamel microhardness (rs=-0.564) and dentin microhardness (rs=-0.356). Genetic factors (DF severity) and the environmental factor (fluoride concentration in tooth structure) have similar influence on tooth biomechanical properties, whereas only the environmental factor has an influence on tooth material property (mineralization).

Urinary fluoride levels and prevalence of dental fluorosis in three Brazilian cities with different fluoride concentrations in the drinking water.

PubMed

Heintze, S D; Bastos, J R; Bastos, R

1998-10-01

Urine samples from three daytime periods were collected from 545 5-50-year-old residents of three different Brazilian cities: Garça had fluoridated drinking water since 1973, Bauru since 1975 and Itápolis was not fluoridated. Dental fluorosis was examined in 985 5-24-year-olds using the Thylstrup-Fejerskov index (TF). The subjects were asked to estimate their daily intake of liquids and frequency of beverage consumption. The analysis of 94 water samples showed high variations in the fluoride content of the drinking water. The mean fluoride concentration of the water samples in Garça was 0.9 mg/L (range 0.75-1.2), in Bauru 0.64 mg/L (range 0.01-1.3), and in Itápolis 0.02 mg/L. Mean urinary fluoride concentration was 1.31 mg/L (s 0.61) in Garça, 0.88 mg/L (s 0.49) in Bauru, and 0.39 mg/L (s 0.21) in Itápolis. Self-reported daily liquid intake was not related to urinary fluoride concentration. The mean prevalence of fluorosis was 13.3% in Garça, 6.8% in Bauru, and 1.7% in Itápolis, with mainly categories TF 1 and TF 2 being recorded. Subjects with dental fluorosis tended to show a higher mean urinary fluoride concentration but the difference was not statistically significant. The study showed that fluoride exposure measured by urinary fluoride excretion was within the range expected for the level of fluoride concentration in the drinking water. However, enamel fluorosis tended to be markedly lower than expected. This study revealed that fluoride levels in the two cities with fluoridated drinking water were variable. To optimise anticaries benefits and minimise the risk of fluorosis greater control of the fluoride dosing of the drinking water is required.

An in vitro evaluation of a novel high fluoride daily mouthrinse using a combination of microindentation, 3D profilometry and DSIMS.

PubMed

Gracia, Louise H; Rees, Gareth D; Brown, Alan; Fowler, Christabel E

2010-11-01

Firstly, to evaluate the in vitro anti-erosion efficacy of a new mouthrinse formulation containing 450 ppm fluoride using profilometry and microindentation. Secondly, to compare fluoride uptake by erosive lesions from two mouthrinses containing different fluoride sources using dynamic secondary ion mass spectrometry (DSIMS). Sound human enamel was treated (60s) with mouthrinses containing different fluoride concentrations, then immersed in 1.0% citric acid pH 3.8 for either 300 s or 30 min (Studies 1 & 2 respectively). Surface roughness and erosion depth were determined profilometrically in Study 1, and surface microhardness monitored as a function of time in Study 2. Lesion rehardening was monitored following a 60 s rinse and immersion in artificial saliva for 48 h (Study 3), whilst Study 4 employed DSIMS to quantify fluoride uptake by lesions treated (60s) with rinses containing either sodium fluoride (NaF) or a NaF/Olaflur/stannous chloride combination. The test rinse (450 ppm fluoride) suppressed surface roughening and bulk tissue loss versus all comparators (p< 0.0001), except in the latter measure for the rinse containing 112 ppm fluoride. The test rinse significantly inhibited enamel surface softening versus the three rinses containing ≤112 ppm fluoride (as NaF) at 30 min (p<0.05), but was not statistically significantly different from the 225 ppm fluoride rinse. The test rinse conferred statistically superior lesion rehardening versus all comparators at both 24 and 48 h (p< 0.0001). DSIMS demonstrated statistically significantly higher fluoride uptake by incipient erosive lesions treated with the test rinse versus the NaF/Olaflur/stannous rinse. Anti-erosion efficacy was positively correlated with fluoride concentration. DSIMS showed significantly higher levels of fluoride uptake by incipient erosive lesions treated with the 450 ppm fluoride rinse versus the NaF/Olaflur/stannous rinse. Copyright © 2010 Elsevier Ltd. All rights reserved.

Utility of check dams in dilution of fluoride concentration in ground water and the resultant analysis of blood serum and urine of villagers, Anantapur District, Andhra Pradesh, India.

PubMed

Bhagavan, S V B K; Raghu, V

2005-02-01

High levels of fluoride (beyond 1.5 ppm) in ground water as source of drinking water are common in many parts of Andhra Pradesh, India, causing fluorosis. The study carried out in endemic Nalgonda District, Andhra Pradesh, has indicated that the fluoride-rich ground water present in the wells located down stream and close to the surface water bodies is getting diluted by the low-fluoride surface water. Encouraged by this result, check dams were constructed upstream of the identified marginally high fluoride bearing ground water zones in Anantapur District to reduce fluoride levels as an alternate solution for safe drinking water. In this paper, an attempt is made to study the utility and effect of these check dams in dilution of fluoride concentration in drinking water and its resultant impact on the health aspects of certain villagers of Anantapur District through the analysis of their blood serum and urine. Ground water samples from three fluoride-affected villages, blood and urine of males and females from the same villages were collected and analyzed for fluoride using ion selective electrode method. The results indicated that the fluoride levels in blood serum and urine of males in the age group of 5-11 years are found to be the highest. The concentration of fluoride in ground water is directly proportional to the concentration of fluoride in blood serum and urine. The concentration of fluoride in ground water with depth of the aquifer is a function of lithology, amount and duration of rainfall, rate of infiltration, level of ground water exploitation in the area etc. The construction of check dams upstream of the identified marginally high fluoride waters will not only cause additional recharge of ground water but also reduces the fluoride concentration eventually improving the health of the villagers.

Composition for detecting uranyl

DOEpatents

Baylor, L.C.; Stephens, S.M.

1994-01-01

The present invention relates to an indicator composition for use in spectrophotometric detection of a substance in a solution, and a method for making the composition. Useful indicators are sensitive to the particular substance being measured, but are unaffected by the fluid and other chemical species that may be present in the fluid. Optical indicators are used to measure the uranium concentration of process solutions in facilities for extracting uranium from ores, production of nuclear fuels, and reprocessing of irradiated fuels. The composition comprises an organohalide covalently bonded to an indicator for the substance, in such a manner that the product is itself an indicator that provides increased spectral resolution for detecting the substance. The indicator is preferably arsenazo III and the organohalide is preferably cyanuric chloride. These form a composition that is ideally suited for detecting uranyl.

Widespread genetic switches and toxicity resistance proteins for fluoride.

PubMed

Baker, Jenny L; Sudarsan, Narasimhan; Weinberg, Zasha; Roth, Adam; Stockbridge, Randy B; Breaker, Ronald R

2012-01-13

Most riboswitches are metabolite-binding RNA structures located in bacterial messenger RNAs where they control gene expression. We have discovered a riboswitch class in many bacterial and archaeal species whose members are selectively triggered by fluoride but reject other small anions, including chloride. These fluoride riboswitches activate expression of genes that encode putative fluoride transporters, enzymes that are known to be inhibited by fluoride, and additional proteins of unknown function. Our findings indicate that most organisms are naturally exposed to toxic levels of fluoride and that many species use fluoride-sensing RNAs to control the expression of proteins that alleviate the deleterious effects of this anion.

Widespread Genetic Switches and Toxicity Resistance Proteins for Fluoride

PubMed Central

Weinberg, Zasha; Roth, Adam; Stockbridge, Randy B.; Breaker, Ronald R.

2014-01-01

Most riboswitches are metabolite-binding RNA structures located in bacterial messenger RNAs where they control gene expression. We have discovered a riboswitch class in many bacterial and archaeal species whose members are selectively triggered by fluoride but reject other small anions, including chloride. These fluoride riboswitches activate expression of genes that encode putative fluoride transporters, enzymes that are known to be inhibited by fluoride, and additional proteins of unknown function. Our findings indicate that most organisms are naturally exposed to toxic levels of fluoride and that many species use fluoride-sensing RNAs to control the expression of proteins that alleviate the deleterious effects of this anion. PMID:22194412

Probability of foliar injury for Acer sp. based on foliar fluoride concentrations.

PubMed

McDonough, Andrew M; Dixon, Murray J; Terry, Debbie T; Todd, Aaron K; Luciani, Michael A; Williamson, Michele L; Roszak, Danuta S; Farias, Kim A

2016-12-01

Fluoride is considered one of the most phytotoxic elements to plants, and indicative fluoride injury has been associated over a wide range of foliar fluoride concentrations. The aim of this study was to determine the probability of indicative foliar fluoride injury based on Acer sp. foliar fluoride concentrations using a logistic regression model. Foliage from Acer nedundo, Acer saccharinum, Acer saccharum and Acer platanoides was collected along a distance gradient from three separate brick manufacturing facilities in southern Ontario as part of a long-term monitoring programme between 1995 and 2014. Hydrogen fluoride is the major emission source associated with the manufacturing facilities resulting with highly elevated foliar fluoride close to the facilities and decreasing with distance. Consistent with other studies, indicative fluoride injury was observed over a wide range of foliar concentrations (9.9-480.0 μg F -  g -1 ). The logistic regression model was statistically significant for the Acer sp. group, A. negundo and A. saccharinum; consequently, A. negundo being the most sensitive species among the group. In addition, A. saccharum and A. platanoides were not statistically significant within the model. We are unaware of published foliar fluoride values for Acer sp. within Canada, and this research provides policy maker and scientist with probabilities of indicative foliar injury for common urban Acer sp. trees that can help guide decisions about emissions controls. Further research should focus on mechanisms driving indicative fluoride injury over wide ranging foliar fluoride concentrations and help determine foliar fluoride thresholds for damage.

Fluoride in drinking water and diet: the causative factor of chronic kidney diseases in the North Central Province of Sri Lanka.

PubMed

Dharmaratne, Ranjith W

2015-07-01

A significant number of people in the North Central Province of Sri Lanka suffer from chronic kidney diseases (CKD), and the author revisits existing literature related to CKD to find its causative factor. There is a direct connection between high fluoride levels in drinking water and kidney disease, and there are unhealthy levels of fluoride in the groundwater in Sri Lanka's CKD-affected areas. Based on the following observations, the author believes with confidence that excess fluoride in drinking water and in the locally grown food in the affected areas are the culprits of CKD in Sri Lanka. Fluoride excretion rate is considerably lower in children than adults, leading to renal damage of children living in areas with high fluoride. Adults who had renal damage due to fluoride in childhood are vulnerable to CKD with continued consumption of water from the same source. Patients with chronic renal insufficiency are at an increased risk of chronic fluoride toxicity. High content of fluoride in groundwater paves the way to excess fluoride in local food crops, consequently adding more fluoride to the systems of the consumers. People who work outdoors for prolonged periods consume excess water and tea, and are subjected to additional doses of fluoride in their system. In the mid-1980s, the increase in water table levels of the affected areas due to new irrigation projects paved the way to adding more fluorides to their system through drinking water and locally grown foods.

The Impact of Selected Fluoridated Toothpastes on Dental Erosion in Profilometric Measurement.

PubMed

Fita, Katarzyna; Kaczmarek, Urszula

2016-01-01

Some fluoridated toothpastes, available commercially, are described to have a protective effect against dental erosion. To evaluate the influence of the selected marketed toothpastes on the human enamel exposed to acid beverages. Enamel specimens from extracted human teeth were prepared (n = 40). Specimens were randomly divided into 10 experimental groups, 4 specimens each, which were subjected to acid challenge for 10 min using orange juice (pH 3.79) or Pepsi Cola (pH 2.58) and then immersed for 2 min into a slurry of five marketed toothpastes with distilled water (1 : 3 w/w). The tested toothpastes contained 1450 or 5000 ppm fluoride, CPP-ACP with 900 ppm fluoride, 1450 ppm fluoride with potassium nitrate 5%, all of them as sodium fluoride, and 700 ppm fluoride as amine and sodium fluoride with 3500 ppm SnCl2. Enamel roughness (Ra parameter) by contact profilometer at baseline and after exposure onto soft drinks and slurry was measured. Exposure to both beverages caused a similar increase of enamel surface roughness. After the specimens immersion into slurries of toothpastes with 1450 or 5000 ppm fluoride, 1450 ppm fluoride with potassium nitrate 5% and CPP-ACP with 900 ppm fluoride the significant decrease of Ra values were found, reaching the baseline values. However, toothpaste with 700 ppm fluoride and 3500 ppm SnCl2 did not cause any fall in Ra value, probably due to other mechanism of action. Within the limitation of the study we can conclude that the sodium fluoride toothpastes are able to restore the surface profile of enamel exposed shortly to acidic soft drinks.

Fluoride and Oral Health.

PubMed

O'Mullane, D M; Baez, R J; Jones, S; Lennon, M A; Petersen, P E; Rugg-Gunn, A J; Whelton, H; Whitford, G M

2016-06-01

The discovery during the first half of the 20th century of the link between natural fluoride, adjusted fluoride levels in drinking water and reduced dental caries prevalence proved to be a stimulus for worldwide on-going research into the role of fluoride in improving oral health. Epidemiological studies of fluoridation programmes have confirmed their safety and their effectiveness in controlling dental caries. Major advances in our knowledge of how fluoride impacts the caries process have led to the development, assessment of effectiveness and promotion of other fluoride vehicles including salt, milk, tablets, toothpaste, gels and varnishes. In 1993, the World Health Organization convened an Expert Committee to provide authoritative information on the role of fluorides in the promotion of oral health throughout the world (WHO TRS 846, 1994). This present publication is a revision of the original 1994 document, again using the expertise of researchers from the extensive fields of knowledge required to successfully implement complex interventions such as the use of fluorides to improve dental and oral health. Financial support for research into the development of these new fluoride strategies has come from many sources including government health departments as well as international and national grant agencies. In addition, the unique role which industry has played in the development, formulation, assessment of effectiveness and promotion of the various fluoride vehicles and strategies is noteworthy. This updated version of 'Fluoride and Oral Health' has adopted an evidence-based approach to its commentary on the different fluoride vehicles and strategies and also to its recommendations. In this regard, full account is taken of the many recent systematic reviews published in peer reviewed literature.

Patterns of dental caries following the cessation of water fluoridation.

PubMed

Maupomé, G; Clark, D C; Levy, S M; Berkowitz, J

2001-02-01

To compare prevalence and incidence of caries between fluoridation-ended and still-fluoridated communities in British Columbia, Canada, from a baseline survey and after three years. At the baseline (1993/4 academic year) and follow-up (1996/7) surveys, children were examined at their schools. Data were collected on snacking, oral hygiene, exposure to fluoride technologies, and socio-economic level. These variables were used together with D1D2MFS indices in multiple regression models. The prevalence of caries (assessed in 5,927 children, grades 2, 3, 8, 9) decreased over time in the fluoridation-ended community while remaining unchanged in the fluoridated community. While numbers of filled surfaces did not vary between surveys, sealed surfaces increased at both study sites. Caries incidence (assessed in 2,994 life-long residents, grades 5, 6, 11, 12) expressed in terms of D1D2MFS was not different between the still-fluoridating and fluoridation-ended communities. There were, however, differences in caries experienced when D1D2MFS components and surfaces at risk were investigated in detail. Regression models did not identify specific variables markedly affecting changes in the incidence of dental decay. Our results suggest a complicated pattern of disease following cessation of fluoridation. Multiple sources of fluoride besides water fluoridation have made it more difficult to detect changes in the epidemiological profile of a population with generally low caries experience, and living in an affluent setting with widely accessible dental services. There are, however, subtle differences in caries and caries treatment experience between children living in fluoridated and fluoridation-ended areas.

Reconstructing temporal variation of fluoride uptake in eastern grey kangaroos (Macropus giganteus) from a high-fluoride area by analysis of fluoride distribution in dentine.

PubMed

Kierdorf, Horst; Rhede, Dieter; Death, Clare; Hufschmid, Jasmin; Kierdorf, Uwe

2016-04-01

Trace element profiling in the incrementally formed dentine of mammalian teeth can be applied to reconstruct temporal variation of incorporation of these elements into the tissue. Using an electron microprobe, this study analysed fluoride distribution in dentine of first and third mandibular molars of free-ranging eastern grey kangaroos inhabiting a high-fluoride area, to assess temporal variation in fluoride uptake of the animals. Fluoride content in the early-formed dentine of first molars was significantly lower than in the late-formed dentine of these teeth, and was also lower than in both, the early and the late-formed dentine of third molars. As early dentine formation in M1 takes place prior to weaning, this finding indicates a lower dentinal fluoride uptake during the pre-weaning compared to the post-weaning period. This is hypothetically attributed to the action of a partial barrier to fluoride transfer from blood to milk in lactating females and a low bioavailability of fluoride ingested together with milk. Another factor contributing to lower plasma fluoride levels in juveniles compared to adults is the rapid clearance of fluoride from blood plasma in the former due to their intense skeletal growth. The combined action of these mechanisms is considered to explain why in kangaroos from high-fluoride areas, the (early-formed) first molars are not affected by dental fluorosis while the (later-formed) third and fourth molars regularly exhibit marked to severe fluorotic lesions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Fluoride Penetration and Clearance Are Higher in Exopolysaccharide-Containing Bacterial Pellets.

PubMed

Spinola, Manuela S; Nóbrega, Diego Figueiredo; Del Bel Cury, Altair Antoninha; Ricomini Filho, Antonio Pedro; Cury, Jaime Aparecido; Tenuta, Livia Maria Andaló

2018-06-06

Extracellular polysaccharides (EPS) could increase the penetration of fluoride through dental biofilm, reducing its cariogenicity. We measured the concentration of fluoride in EPS-containing (EPS+) or not-containing (EPS-) Streptococcus mutans bacterial pellets resembling test biofilms, before and up to 60 min after a 0.05% NaF rinse in situ. Fluoride penetration and clearance were higher in EPS+ bacterial pellets. The data suggest that EPS enhances fluoride penetration, but also accelerates fluoride clearance from dental biofilms. © 2018 S. Karger AG, Basel.

Fungus hyphae-supported alumina: An efficient and reclaimable adsorbent for fluoride removal from water.

PubMed

Yang, Weichun; Tian, Shunqi; Tang, Qiongzhi; Chai, Liyuan; Wang, Haiying

2017-06-15

A reclaimable adsorbent of fungus hyphae-supported alumina (FHSA) bio-nanocomposites was developed, characterized and applied in fluoride removal from water. This adsorbent can be fast assembled and disassemble reversibly, promising efficient reclamation and high accessible surface area for fluoride adsorption. Adsorption experiments demonstrate that the FHSA performed well over a considerable wide pH range of 3-10 with high fluoride removal efficiencies (>66.3%). The adsorption capacity was 105.60mgg -1 for FHSA, much higher than that for the alumina nanoparticles (50.55mgg -1 ) and pure fungus hyphae (22.47mgg -1 ). The adsorption capacity calculated by the pure content of alumina in the FHSA is 340.27mgg -1 of alumina. Kinetics data reveal that the fluoride adsorption process on the FHSA was fast, nearly 90% fluoride adsorption can be achieved within 40min. The fluoride adsorption on the FHSA is mainly due to the surface complexes formation of fluoride with AlOH and the attraction between protonated NH 2 and fluoride through hydrogen bonding. Findings demonstrate that the FHSA has potential applicability in fluoride removal due to its strong fluoride adsorbility and the easy reclamation by its fast reversible assembly and disassembly feature. Copyright © 2017 Elsevier Inc. All rights reserved.

Daily Fluoride Intake from Iranian Green Tea: Evaluation of Various Flavorings on Fluoride Release

PubMed Central

Maleki, Afshin; Daraei, Hiua; Mohammadi, Elham; Zandi, Shiva; Teymouri, Pari; Mahvi, Amir Hossien; Gharibi, Fardin

2016-01-01

With increased awareness of the health benefits of the compounds in green tea, especially polyphenols, its consumption is rising. The main purpose of this study is to determine the effect of different additives on the released fluoride into tea liquor and also daily fluoride intake. The concentrations of fluoride, nitrate, sulfate, and chloride were measured in 15 different flavored green teas (Refah-Lahijan). The fluoride and other anion concentrations were measured by ion chromatography method. The data were analyzed with Statistical Package for the Social Sciences version 16.0. The results showed that the minimum and maximum concentrations of fluoride in the green tea infusions were 0.162 mg/L (cinnamon-flavored green tea) and 3.29 mg/L (bagged peach-flavored green tea), respectively. The mean concentration of fluoride in the green tea leaves was 52 mg/kg, and approximately 89% of the fluoride was released from the green tea leaves into the infusions after brewing. The fluoride concentrations varied significantly among the examined green teas (P < 0.05). However, the additives had no significant effect on the fluoride release into the infusions (P > 0.05). Finally, drinking of the studied green teas cannot make a significant contribution to the daily dietary intake of F for consumers. PMID:27042093

Daily Fluoride Intake from Iranian Green Tea: Evaluation of Various Flavorings on Fluoride Release.

PubMed

Maleki, Afshin; Daraei, Hiua; Mohammadi, Elham; Zandi, Shiva; Teymouri, Pari; Mahvi, Amir Hossien; Gharibi, Fardin

2016-01-01

With increased awareness of the health benefits of the compounds in green tea, especially polyphenols, its consumption is rising. The main purpose of this study is to determine the effect of different additives on the released fluoride into tea liquor and also daily fluoride intake. The concentrations of fluoride, nitrate, sulfate, and chloride were measured in 15 different flavored green teas (Refah-Lahijan). The fluoride and other anion concentrations were measured by ion chromatography method. The data were analyzed with Statistical Package for the Social Sciences version 16.0. The results showed that the minimum and maximum concentrations of fluoride in the green tea infusions were 0.162 mg/L (cinnamon-flavored green tea) and 3.29 mg/L (bagged peach-flavored green tea), respectively. The mean concentration of fluoride in the green tea leaves was 52 mg/kg, and approximately 89% of the fluoride was released from the green tea leaves into the infusions after brewing. The fluoride concentrations varied significantly among the examined green teas (P < 0.05). However, the additives had no significant effect on the fluoride release into the infusions (P > 0.05). Finally, drinking of the studied green teas cannot make a significant contribution to the daily dietary intake of F for consumers.

Tissue distributions of fluoride and its toxicity in the gills of a freshwater teleost, Cyprinus carpio.

PubMed

Cao, Jinling; Chen, Jianjie; Wang, Jundong; Wu, Xiangtian; Li, Yundong; Xie, Lingtian

2013-04-15

Fish take up fluoride directly from water and are susceptible to fluoride contamination of their environment. In this study, we examined the tissue distributions of fluoride and its toxicity in the gills of the common carp (Cyprinus carpio) chronically exposed to fluoride. Carp were exposed to a range of aqueous fluoride (35-124 mg/L) and sampled at 30, 60 and 90 days. The accumulation of fluoride in the tissues increased with the level and duration of exposure. Steady state was not achieved under the experimental conditions. The gills accumulated the highest levels of fluoride followed by the liver>brain>kidney>muscle>intestine. A dose-dependent inhibition was observed for the enzyme activities of Na(+)-K(+)-ATPase and Ca(2+)-ATPase in the gills after the fish were exposed for 90 days. Also, accumulation of fluoride was associated with the inhibition of superoxide dismutase (SOD) activities and a dose-dependent stimulation of malondialdehyde (MDA) levels in the gill tissues, suggesting that fluoride promoted oxidative stress in the fish. Microscopic examinations revealed injuries to gill tissues and chloride cells, with the severity of injury increasing with exposure concentration. These results suggest that chronic exposure to elevated concentrations of fluoride may induce toxicity in the common carp. Copyright © 2012 Elsevier B.V. All rights reserved.

Toxicity of fluoride to microorganisms in biological wastewater treatment systems.

PubMed

Ochoa-Herrera, Valeria; Banihani, Qais; León, Glendy; Khatri, Chandra; Field, James A; Sierra-Alvarez, Reyes

2009-07-01

Fluoride is a common contaminant in a variety of industrial wastewaters. Available information on the potential toxicity of fluoride to microorganisms implicated in biological wastewater treatment is very limited. The objective of this study was to evaluate the inhibitory effect of fluoride towards the main microbial populations responsible for the removal of organic constituents and nutrients in wastewater treatment processes. The results of short-term batch bioassays indicated that the toxicity of sodium fluoride varied widely depending on the microbial population. Anaerobic microorganisms involved in various metabolic steps of anaerobic digestion processes were found to be very sensitive to the presence of fluoride. The concentrations of fluoride causing 50% metabolic inhibition (IC(50)) of propionate- and butyrate-degrading microorganisms as well as mesophilic and thermophilic acetate-utilizing methanogens ranged from 18 to 43 mg/L. Fluoride was also inhibitory to nitrification, albeit at relatively high levels (IC(50)=149 mg/L). Nitrifying bacteria appeared to adapt rapidly to fluoride, and a near complete recovery of their metabolic activity was observed after only 4d of exposure to high fluoride levels (up to 500 mg/L). All other microbial populations evaluated in this study, i.e., glucose fermenters, aerobic glucose-degrading heterotrophs, denitrifying bacteria, and H(2)-utilizing methanogens, tolerated fluoride at very high concentrations (>500 mg/L).

[The effects of topical fluoridation of Ketac Molar Aplicap glass-ionomer material on the growth of cariogenic bacteria contained in the dental plaque].

PubMed

Płuciennik-Stronias, Małgorzata; Zarzycka, Beata; Bołtacz-Rzepkowska, Elzbieta

2013-01-01

Dental caries is a bacterial disease. The most important element used in caries prevention is fluoride, which is derived from the air, diet or fluoride-containing preparations and materials, e.g. glass-ionomer restorations. Modern fluoride-containing restorative materials are capable of releasing fluoride to the environment. Fluoride can be also accumulated in glass-ionomer cements, thus an attempt was made to saturate these materials with fluoride. The aim of the study was to evaluate the effect of topical fluoridation of Ketac Molar Aplicap glass-ionomer cement on the growth of Lactobacillus spp. in the dental plaque. The study was carried out in 15 patients with good oral hygiene, in whom 35 fillings with conventional glass-ionomer material, Ketac Molar Aplicap, were performed. After 6 months, three-day dental plaque from these fillings was examined. Next, fluoride was rubbed on the glass-ionomer surface and the examination of three-day dental plaque was repeated. No statistically significant differences (p = 0.143) in the amounts of Lactobacillus spp. in the plaque collected prior to and after topical fluoridation were revealed. Fluoride rubbed in the conventional glass-ionomer cement, Ketac Molar Aplicap, did not affect the amount of Lactobacillus spp. in the dental plaque growing on this material.

Fluoride content of clay minerals and argillaceous earth materials

USGS Publications Warehouse

Thomas, Josephus; Glass, H.D.; White, W.A.; Trandel, R.M.

1977-01-01

A reliable method, utilizing a fluoride ion-selective electrode, is described for the determination of fluoride in clays and shales. Interference by aluminum and iron is minimal. The reproducibility of the method is about ±5% at different levels of fluoride concentration.Data are presented for various clay minerals and for the <2-µm fractions of marine and nonmarine clays and shales. Fluoride values range from 44 ppm (0.0044%) for nontronite from Colfax, WA, to 51,800 ppm (5.18%) for hectorite from Hector, CA. In general, clays formed under hydrothermal conditions are relatively high in fluoride content, provided the hydrothermal waters are high in fluoride content. Besides hectorite, dickite from Ouray, CO, was found to contain more than 50 times as much fluoride (6700 ppm) as highly crystalline geode kaolinite (125 ppm). The clay stratum immediately overlying a fluorite mineralized zone in southern Illinois was found to have a higher fluoride content than the same stratum in a nonmineralized zone approximately 1 mile away. Nonmarine shales in contact with Australian coals were found to be lower in fluoride content than were marine shales in contact with Illinois coals.It is believed that, in certain instances, peak shifts on DTA curves of similar clay minerals are the result of significant differences in their fluoride content.

Associations between exposure to fluoridated drinking water and dental caries experience among children in two Australian states.

PubMed

Slade, G D; Davies, M J; Spencer, A J; Stewart, J F

1995-01-01

This study assessed associations between exposure to fluoride in water and dental caries experience among children in two Australian states. Cross-sectional data were obtained from 9,690 South Australian children aged 5-15 years and 10,195 Queensland children aged 5-12 years. School dental service practitioners recorded DMFS and dmfs data. A questionnaire to parents gained information about residential history that was used to calculate children's percent of lifetime exposed to fluoridated water. Greater exposure to fluoride in water was associated with lower dmfs and DMFS in both states (P < .01), although in South Australia the effect for DMFS was statistically significant only after controlling for extent of unknown fluoridation exposure and for fluoride supplements. Caries-fluoridation associations were stronger for dmfs compared with DMFS and for Queensland (5% of population fluoridated) compared with South Australia (70% of population fluoridated). Effects for DMFS persisted after controlling for socioeconomic factors. Fluoridation was associated with lower caries experience. The weaker association with DMFS in South Australia may be due to less caries and more fissure sealants in that state, and is consistent with a "diffusion" effect, whereby a high proportion of the population exposed to fluoridation diminishes differences among exposure groups.

Effects of different amine fluoride concentrations on enamel remineralization.

PubMed

Naumova, E A; Niemann, N; Aretz, L; Arnold, W H

2012-09-01

The aim of this study was to investigate the effects of decreasing fluoride concentrations on repeated demineralizing challenges on human enamel. In 24 teeth, 3mm×3mm windows were prepared on the buccal and lingual sides and treated in a cycling demineralization-remineralization model. Remineralization was achieved with 100, 10 and 0.1 ppm fluoride from anime fluoride. Coronal sections were cut through the artificial lesions, and three sections per tooth were investigated using polarized light microscopy and scanning electron microscopy with quantitative element analysis. The morphology of the lesions was studied, and the extensions of the superficial layer and the body of the lesion were measured. Using element analysis, the Ca, P and F content were determined. The body of the lesion appeared remineralized after application of 100 ppm fluoride, while remineralization of the lesion was less successful after application of 10 and 0.1 ppm fluoride. The thickness of the superficial layer increased with decreasing fluoride concentrations, and also the extension of the body of the lesion increased. Ca and P content increased with increasing fluoride concentrations. The effectiveness of fluoride in enamel remineralization increased with increasing fluoride concentration. A consistently higher level of fluoride in saliva should be a goal in caries prevention. Copyright © 2012 Elsevier Ltd. All rights reserved.

Modelling of fluoride removal via batch monopolar electrocoagulation process using aluminium electrodes

NASA Astrophysics Data System (ADS)

Amri, N.; Hashim, M. I.; Ismail, N.; Rohman, F. S.; Bashah, N. A. A.

2017-09-01

Electrocoagulation (EC) is a promising technology that extensively used to remove fluoride ions efficiently from industrial wastewater. However, it has received very little consideration and understanding on mechanism and factors that affecting the fluoride removal process. In order to determine the efficiency of fluoride removal in EC process, the effect of operating parameters such as voltage and electrolysis time were investigated in this study. A batch experiment with monopolar aluminium electrodes was conducted to identify the model of fluoride removal using empirical model equation. The EC process was investigated using several parameters which include voltage (3 - 12 V) and electrolysis time (0 - 60 minutes) at a constant initial fluoride concentration of 25 mg/L. The result shows that the fluoride removal efficiency increased steadily with increasing voltage and electrolysis time. The best fluoride removal efficiency was obtained with 94.8 % removal at 25 mg/L initial fluoride concentration, voltage of 12 V and 60 minutes electrolysis time. The results indicated that the rate constant, k and number of order, n decreased as the voltage increased. The rate of fluoride removal model was developed based on the empirical model equation using the correlation of k and n. Overall, the result showed that EC process can be considered as a potential alternative technology for fluoride removal in wastewater.

Laboratory investigations into the potential anticaries efficacy of fluoride varnishes.

PubMed

Lippert, Frank; Hara, Anderson Takeo; Martinez-Mier, Esperanza Angeles; Zero, Domenick T

2014-01-01

The purpose of this study was to investigate the potential anticaries efficacy of fluoride varnishes (FVs) by studying their ability to reharden and deliver fluoride to carious lesions and to release fluoride into saliva. Enamel carious lesions were created and allocated to 24 groups (11 FVs with two FV incubation times and two control groups) based on Knoop microhardness test values. FVs were applied to lesions, which were incubated in artificial saliva for two or six hours, with saliva being renewed hourly. FV was removed and lesions were remineralized in artificial saliva for 22 hours. Microhardness was measured and enamel fluoride uptake (EFU) was determined. Saliva samples (six-hour groups) were analyzed to determine fluoride release characteristics. Data were analyzed using analysis of variance. FVs differed considerably in their ability to reharden and deliver fluoride to carious lesions and in their fluoride release characteristics. Little consistency was found between investigated study variables for virtually all tested FVs. For example, a particular FV showed the highest EFU and fluoride release values but the lowest rehardening value. A longer FV contact time led to increased EFU for five of the 11 FVs. Some FVs delivered more fluoride to lesions in two hours than others did in six hours. Fluoride varnishes differ greatly in their in vitro anticaries efficacy.

Changing risk factors for fluorosis among South Australian children.

PubMed

Spencer, A John; Do, Loc G

2008-06-01

Research in the last decade has shown changing exposure patterns to discretionary fluorides and declining prevalence of fluorosis among South Australian children, raising the question of how risk factors for fluorosis have changed. To examine and compare risk factors for fluorosis among representative samples of South Australian children in 1992/1993 and 2002/2003. Similar sampling strategies and data collection methods were employed in the Child Fluoride Study (CFS) Marks 1 (1992/1993) and 2 (2002/2003). Participants in each CFS round were examined for fluorosis using the Thylstrup and Fejerskov (TF) Index. Exposure history was collected for fluoride in water, toothpaste, fluoride supplements and infant formula, allowing for a fluorosis risk assessment analysis. Data were re-weighted to represent the child population at each time. Changes in prevalence of fluorosis, defined as having a TF score of 1+ on maxillary central incisors, fluoride exposure and risk factors between the two rounds were evaluated. A total of 375 and 677 children participated in the 1992/1993 and 2002/2003 rounds respectively. Prevalence of fluorosis declined significantly from 45.3% to 25.9%. Reduced use of fluoride supplements and increased use of 400-550-ppm children F toothpaste were the most substantial fluoride exposure changes. Early toothpaste use, residence in fluoridated areas and fluoride supplement use were the risk factors in 1992/1993. Early toothpaste use and fluoride supplement use were not risk factors, leaving fluoridated water as the only risk factor among the common variables in 2002/2003. In an analysis stratified by the type of fluoridated toothpaste in 2002/2003, the large amount of toothpaste used was a risk factor in those who used 1000-ppm fluoridated toothpaste, and eating/licking toothpaste when toothpaste use started was a risk factor among children who used either 1000-ppm or 400-550-ppm fluoridated toothpaste. Introduction of the 400-550-ppm F toothpaste and use of smaller amount of toothpaste restricted risk associated with early toothpaste use. Less use and possibly a stricter fluoride supplements regimen also restricted fluorosis risk. Periodic monitoring of risk of fluorosis is required to adjust guidelines for fluoride use in caries prevention.

Fluoride Programs in the School Setting: Preventive Dental Health.

ERIC Educational Resources Information Center

Rebich, Theodore, Jr.; And Others

1982-01-01

Two types of school-based programs that increase students' use of fluoride for preventive dental health are described. In fluoride mouthrinse programs, teachers give their students a fluoride solution once a week in a paper cup. In areas where the level of fluoride in the water supply is insufficient, the flouride tablet program is used. (JN)

High School Forum.

ERIC Educational Resources Information Center

Herron, J. Dudley, Ed.

1980-01-01

Presents questions and answers about the fluoridation of water regarding the compounds added to drinking water in the fluoridation process, how raw water is tested for fluoride content, and how fluoride reacts with tooth enamel. (CS)

Mitigation of Fluorosis - A Review

PubMed Central

Dodamani, Arun S.; Jadhav, Harish C.; Naik, Rahul G.; Deshmukh, Manjiri A.

2015-01-01

Fluoride is required for normal development and growth of the body. It is found in plentiful quantity in environment and fluoride content in drinking water is largest contributor to the daily fluoride intake. The behaviour of fluoride ions in the human organism can be regarded as that of “double-edged sword”. Fluoride is beneficial in small amounts but toxic in large amounts. Excessive consumption of fluorides in various forms leads to development of fluorosis. Fluorosis is major health problem in 24 countries, including India, which lies in the geographical fluoride belt. Various technologies are being used to remove fluoride from water but still the problem has not been rooted out. The purpose of this paper is to review the available treatment modalities for fluorosis, available technologies for fluoride removal from water and ongoing fluorosis mitigation programs based on literature survey. Medline was the primary database used in the literature search. Other databases included: PubMed, Web of Science, Google Scholar, WHO, Ebscohost, Science Direct, Google Search Engine, etc. PMID:26266235

Total and Free Fluoride Concentration in Various Brands of Toothpaste Marketed in India

PubMed Central

Siddanna, Sunitha

2015-01-01

Background For fluoridated toothpaste to be effective in controlling dental caries, an adequate concentration of soluble fluoride must be available in the oral cavity. Aim To determine the total and free fluoride concentration in various brands of toothpaste marketed in India. Materials and Methods Three samples of 12 different toothpastes were purchased from supermarkets in Mysore city, Karnataka, India. Toothpastes were analysed in duplicate using a fluoride ion-specific electrode. The concentration of total fluoride (TF) and total soluble fluoride (TSF) were determined. Results Measured TF was consistent with that declared by the manufacturer in five products. Four toothpastes showed lower TF and two higher TF than declared. Most toothpastes exhibited TSF concentrations similar to the TF content except four samples that displayed considerably lower TSF than TF. Conclusion The measurement of total and free fluoride concentrations of toothpastes available in India showed inhomogenities. Therefore there is a need for stringent regulatory control measures for the determination of fluoride content in toothpastes in developing country like India. PMID:26557607

Fluoride Increases Superoxide Production and Impairs the Respiratory Chain in ROS 17/2.8 Osteoblastic Cells

PubMed Central

Fina, Brenda Lorena; Lombarte, Mercedes; Rigalli, Juan Pablo; Rigalli, Alfredo

2014-01-01

It is known that fluoride produces oxidative stress. Inflammation in bone tissue and an impairment of the respiratory chain of liver have been described in treatments with fluoride. Whether the impairment of the respiratory chain and oxidative stress are related is not known. The aim of this work was to study the effects of fluoride on the production of superoxide radical, the function of the respiratory chain and the increase in oxidative stress in ROS 17/2.8 osteoblastic cells. We measured the effect of fluoride (100 µM) on superoxide production, oxygen consumption, lipid peroxidation and antioxidant enzymes activities of cultured cells following the treatment with fluoride. Fluoride decreased oxygen consumption and increased superoxide production immediately after its addition. Furthermore, chronic treatment with fluoride increased oxidative stress status in osteoblastic cells. These results indicate that fluoride could damage bone tissue by inhibiting the respiratory chain, increasing the production of superoxide radicals and thus of the others reactive oxygen species. PMID:24964137

Effect of fluoride mouthwash on tensile strength of stainless steel orthodontic archwires

NASA Astrophysics Data System (ADS)

Fatimah, D. I.; Anggani, H. S.; Ismah, N.

2017-08-01

Patients with orthodontic treatment are commonly recommended to use a fluoride mouthwash for maintaining their oral hygiene and preventing dental caries. However, fluoride may affect the characteristics of stainless steel orthodontic archwires used during treatment. The effect of fluoride mouthwash on the tensile strength of stainless steel orthodontic archwires is still unknown. The purpose of this study is to know the effect of fluoride mouthwash on the tensile strength of stainless steel orthodontic archwires. Examine the tensile strength of 0.016 inch stainless steel orthodontic archwires after immersion in 0.05%, 100 ml fluoride mouthwash for 30, 60, and 90 min. There is no statistically significant difference in the tensile strength of stainless steel orthodontic archwires after immersed in fluoride mouthwash. The p-values on immersion fluoride mouthwash for 30, 60, and 90 min consecutively are 0.790; 0.742; and 0.085 (p > 0.05). The use of fluoride mouthwash did not have an effect on the tensile strength of stainless Steel orthodontic archwires.

The effects of sodium fluoride and stannous fluoride on the surface roughness of intraoral magnet systems.

PubMed

Obatake, R M; Collard, S M; Martin, J; Ladd, G D

1991-10-01

Four types of intraoral magnets used for retention of overdentures and maxillofacial prostheses were exposed in vitro to SnF2 and NaF to determine the effects of fluoride rinses on surface roughness. The surface roughness (Ra) was measured, after simulated 1, 2, and 5 years' clinical exposure to fluoride (31, 62, and 155 hours). The mean change in Ra was calculated for each period of simulated exposure to fluoride for each magnet type. Two-way ANOVA was used to compare mean change in Ra between magnets within fluorides, and between fluorides within magnets. Paired t tests were used to compare mean change in Ra within fluorides within magnets. The mean change in Ra increased for all magnets after simulated 1, 2, and 5 years of exposure to SnF2 and NaF (p less than 0.03). Using the change in Ra as an indicator for corrosion, PdCo encapsulated SmCo5 magnets and their keepers demonstrated the least corrosion with either fluoride.

Fluoride and Water (For Parents)

MedlinePlus

... the label. The Controversy Over Fluoride Opponents of water fluoridation have questioned its safety and effectiveness; however, there has been little evidence to support these concerns. Scientific research continues to show the benefits of fluoride when ...

FLUORIDE CONTENT OF COMMERCIALLY AVAILABLE SOY MILK PRODUCTS IN THAILAND.

PubMed

Rirattanapong, Opas; Rirattanapong, Praphasri

2016-01-01

Abstract. In Thailand, the consumption of soy milk products is common but there is limited data about their fluoride content. The purpose of this study was to es- timate the fluoride content of soy milk products available in Thailand. Fluoride content was determined for 76 brands of soy milk using a F-ion-specific electrode. The fluoride concentrations ranged from 0.01 to 3.78 μg/ml. The fluoride content was not related to sugar content, soy bean content or the sterilization process. Among 3 brands of soy milk containing tea powder extract, the fluoride content was high (1.25 to 3.78 μg/ml). Most brands of soy milk tested in our study had fluoride content below the optimal daily intake but brands containing tea powder extract if consumed by children may increase their risk for fluorosis.

METHOD OF SEPARATING PLUTONIUM

DOEpatents

Brown, H.S.; Hill, O.F.

1958-02-01

Plutonium hexafluoride is a satisfactory fluorinating agent and may be reacted with various materials capable of forming fluorides, such as copper, iron, zinc, etc., with consequent formation of the metal fluoride and reduction of the plutonium to the form of a lower fluoride. In accordance with the present invention, it has been found that the reactivity of plutonium hexafluoride with other fluoridizable materials is so great that the process may be used as a method of separating plutonium from mixures containing plutonium hexafluoride and other vaporized fluorides even though the plutonium is present in but minute quantities. This process may be carried out by treating a mixture of fluoride vapors comprising plutonium hexafluoride and fluoride of uranium to selectively reduce the plutonium hexafluoride and convert it to a less volatile fluoride, and then recovering said less volatile fluoride from the vapor by condensation.

Risk perception, psychological heuristics and the water fluoridation controversy.

PubMed

Perrella, Andrea M L; Kiss, Simon J

2015-04-29

Increasingly, support for water fluoridation has come under attack. We seek an explanation, focusing on the case of Waterloo, Ontario, where a 2010 referendum overturned its water fluoridation program. In particular, we test whether individuals perceive the risks of water fluoridation based not on 'hard' scientific evidence but on heuristics and cultural norms. A sample of 376 residents in Waterloo were surveyed in June 2012 using random digit dialing. We use factor analysis, OLS regression, as well as t-tests to evaluate a survey experiment to test the credibility hypothesis. Perceptions of fluoride as a risk are lower among those who perceive fluoride's benefits (B = .473, p < 0.001) and those whose cultural view is 'egalitarian' (B = .156, p < 0.05). The experiment shows a lower level of perception of fluoride's benefits among respondents who are told that water fluoridation is opposed by a national advocacy group (Group A) compared to those who are told that the government and the World Health Organization support fluoridation (Group B) (t = 1.6547, p < 0.05), as well as compared to the control group (t = 1.8913, p < 0.05). There is no difference between Group B and the control, possibly because people's already general support for fluoridation is less prone to change when told that other public organizations also support fluoridation. Public health officials should take into account cultural norms and perceptions when individuals in a community appear to rise up against water fluoridation, with implications for other public health controversies.

Bioavailability of fluoride in drinking water: a human experimental study.

PubMed

Maguire, A; Zohouri, F V; Mathers, J C; Steen, I N; Hindmarch, P N; Moynihan, P J

2005-11-01

It has been suggested that systemic fluoride absorption from drinking water may be influenced by the type of fluoride compound in the water and by water hardness. Using a human double-blind cross-over trial, we conducted this study to measure c(max), T(max), and Area Under the Curve (AUC) for plasma F concentration against time, following the ingestion of naturally fluoridated hard and soft waters, artificially fluoridated hard and soft waters, and a reference water. Mean AUC over 0 to 8 hours was 1330, 1440, 1679, 1566, and 1328 ng F.min.mL(-1) for naturally fluoridated soft, naturally fluoridated hard, artificially fluoridated soft, artificially fluoridated hard, and reference waters, respectively, with no statistically significant differences among waters for AUC, c(max), or T(max). Any differences in fluoride bioavailability between drinking waters in which fluoride is present naturally or added artificially, or the waters are hard or soft, were small compared with large within- and between-subject variations in F absorption. Abbreviations used: F, fluoride; AUC, Area under the Curve for plasma F concentration against time; AUC(0-3), Area under the Curve for plasma F concentration against time for 0 to 3 hours following water ingestion; AUC(0-8), Area under the Curve for plasma F concentration against time for 0 to 8 hours following water ingestion; c(max), maximum plasma F concentration corrected for baseline plasma F and dose (i.e., F concentration of individual waters); T(max), time of c(max).

Is there a need of extra fluoride in children?

PubMed

Gupta, Sunil Kumar; Gupta, R C; Gupta, A B

2009-09-01

The issues related to fluoridation of water or fortification of tooth paste with compounds of fluorides are controversial. Fluoride is stored mainly in the bones, where it increases the density and changes the internal architecture, makes it osteoporotic and more prone to fractures. Fluoride consumption by human beings increases the general cancer death rate, disrupts the synthesis of collagen and leads to the breakdown of collagen in bone, tendon, muscle, skin, cartilage, lungs, kidney and trachea, causing disruptive effect on various tissues in the body. It inhibits antibody formation, disturbs immune system and makes the child prone to malignancy. Fluoride has been categorized as a protoplasmic poison and any additional ingestion of fluoride by children is undesirable.

SEPARATION OF PROTACTINIUM FROM MOLTEN SALT REACTOR FUEL COMPOSITIONS

DOEpatents

Shaffer, J.H.; Strain, J.E.; Cuneo, D.R.; Kelly, M.J.

1963-11-12

A method for selectively precipitating protactinium from a neutron- irradiated fused fluoride salt composition comprising at least one metal fluoride selected from the group consisting of an alkali metal fluoride and an alkaline earth metal fluoride containing dissolved thorium-232 values is presented. An inorganic metal oxide corresponding to any of the metal fluorides of the composition is also added. (AEC)

[Geographical distribution of fluoride in the public water supply in the province of Tucumán, Argentina].

PubMed

Durán, Raúl Alberto; Durán, Estela Liliana; Ojeda, Graciela de Jesús; Castellanos, Walter Alfredo

2017-01-01

This work studied the geographical distribution of fluoride content in the public water supply in the province of Tucumán, Argentina. A total of 1,210 samples were collected in 190 localities of the 17 departments of the province during the 2008-2012 period. The analytical determination was performed using the SPADNS method and QGis 2.16 was used for processing the information. The fluoride content requirements in the studied localities were determined according to the Argentine Food Code. The results showed that 94% of population studied consumed water with fluoride concentrations below the recommended limits, 5% were exposed to fluoride concentrations above the required maximum limit and 1% consumed water at optimal fluoride concentrations. The maps showed a heterogeneous geographical distribution of fluorides, in which areas with deficit, excess and recommended values of fluorides can be differentiated; in some departments an inverse relationship between the density of the hydrological network and fluoride concentration can be observed. In the capital of the province, the average value found was 0.32 mg/l, presenting a homogeneous geographical distribution. The information obtained is indispensable for the proper management of fluoride, so as to improve public health through policy.

Reducing Exposure to High Fluoride Drinking Water in Estonia—A Countrywide Study

PubMed Central

Indermitte, Ene; Saava, Astrid; Karro, Enn

2014-01-01

Fluoride is a naturally occurring contaminant in groundwater in Estonia. There are several regions in Estonia with fluoride contents in public water supplies as high as 7 mg/L. Long-term exposure to high-fluoride drinking water may have several adverse health effects, primarily dental fluorosis. The opportunities for exposure reduction rely highly on water treatment technologies. Since 2004 public water suppliers in Estonia have made efforts to diminish fluoride content in drinking water systems. A follow-up study on a country level was carried out in 2004–2012 to analyze the changes in population exposure to excessive (over 1.5 mg/L) fluoride in drinking water and to get information about the reduction methods applied by public water supplies (PWS) to optimize the fluoride levels in public water system. The results showed that bigger PWS have been more effective in fluoride reduction measures than small PWS. The main methods used to lower the fluoride content were reverse osmosis technology and replacement of water sources with new ones (new drilled wells). As a result of all the measures taken the overall high-fluoride exposure has been reduced substantially (82%). PMID:24637908

Characterization of a fluoride-resistant bacterium Acinetobacter sp. RH5 towards assessment of its water defluoridation capability

NASA Astrophysics Data System (ADS)

Mukherjee, Shraboni; Yadav, Vaibhav; Mondal, Madhumanti; Banerjee, Soumya; Halder, Gopinath

2017-07-01

The present study investigates the defluoridation capability of fluoride-resistant bacteria from contaminated groundwater collected from Asanjola and Madhabpur, West Bengal, India. Seven strains of fluoride-resistant bacteria were isolated employing culture media containing 10-250 mg/L of fluoride to evaluate their ability in reducing fluoride concentration in water. Five isolates exhibited significant amount of reduction in fluoride. Isolate RH5 achieved a maximum fluoride removal of 25.7 % from the media at 30 °C and pH 7 after 8 days of incubation. Based on morphological, physiological characteristics and analysis of 16S rDNA gene sequence, isolate RH5 was identified as Acinetobacter sp. RH5. Growth of RH5 was analysed at a diverse pH range, and it could thrive at pH 5-10. The present investigation revealed that the selective pressure of fluoride results in growth of fluoride-resistant bacteria capable of secreting high-affinity anion-binding compounds. This bacterium played a dominant bioremediative role by concentrating the anions so that they become less available. Hence, the fluoride-resistant bacteria, Acinetobacter sp. RH5, could be used as a promising strain for application in water defluoridation from contaminated sites.

Reducing exposure to high fluoride drinking water in Estonia-a countrywide study.

PubMed

Indermitte, Ene; Saava, Astrid; Karro, Enn

2014-03-14

Fluoride is a naturally occurring contaminant in groundwater in Estonia. There are several regions in Estonia with fluoride contents in public water supplies as high as 7 mg/L. Long-term exposure to high-fluoride drinking water may have several adverse health effects, primarily dental fluorosis. The opportunities for exposure reduction rely highly on water treatment technologies. Since 2004 public water suppliers in Estonia have made efforts to diminish fluoride content in drinking water systems. A follow-up study on a country level was carried out in 2004-2012 to analyze the changes in population exposure to excessive (over 1.5 mg/L) fluoride in drinking water and to get information about the reduction methods applied by public water supplies (PWS) to optimize the fluoride levels in public water system. The results showed that bigger PWS have been more effective in fluoride reduction measures than small PWS. The main methods used to lower the fluoride content were reverse osmosis technology and replacement of water sources with new ones (new drilled wells). As a result of all the measures taken the overall high-fluoride exposure has been reduced substantially (82%).

Geographical mapping of fluoride levels in drinking water sources in Nigeria.

PubMed

Akpata, Enosakhare S; Danfillo, I S; Otoh, E C; Mafeni, J O

2009-12-01

Knowledge of fluoride levels in drinking water is of importance in dental public health, yet this information is lacking, at national level, in Nigeria. To map out fluoride levels in drinking water sources in Nigeria. Fluoride levels in drinking water sources from 109 randomly selected Local Government Areas (LGAs) in the 6 Nigerian geopolitical zones were determined. From the results, maps showing LGAs with fluoride concentrations exceeding 0.3 ppm, were drawn. ANOVA and t-test were used to determine the significance of the differences between the fluoride levels in the drinking water sources. Fluoride levels were low in most parts of the country, being 0.3 ppm or less in 62% of the LGAs. Fluoride concentrations were generally higher in North Central geopolitical zone, than the other zones in the country (p<0.05). In a few drinking water sources, fluoride concentrations exceeded 1.5 ppm, but was as high as 6.7 ppm in one well. Only 9% of the water sources were from waterworks. Most of the water sources in Nigeria contained low fluoride levels; but few had excessive concentrations and need to be partially defluoridated, or else alternative sources of drinking water provided for the community.

The influence of age on the distribution, metabolism and excretion of methoxyflurane in Fischer 344 rats: a possible relationship to nephrotoxicity.

PubMed

Bell, L E; Hitt, B A; Mazze, R I

1975-10-01

Age as a factor in methoxyflurane nephrotoxicity was evaluated in Fischer 344 rats of various ages by determination of: 1) serum inorganic fluoride and methoxyflurane concentrations, and urinary inorganic fluoride excretion in methoxyflurane-exposed rats; 2) liver microsomal methoxyflurane defluorinase activity; and 3) distribution of injected sodium fluoride. Only rats in the youngest age group (6 weeks) did not develop nephrotoxicity after anesthesia. Older rats had a biphasic rather than a monophasic decay in serum methoxyflurane concentration and also had increased serum inorganic fluoride concentration and urinary inorganic fluoride excretion. Older rats also excreted a greater proportion of an injected dose of sodium fluoride compared to young rats. Microsomal methoxyflurane defluorinase specific activity was similar among rats of all ages. It is likely that increased availability of methoxyflurane due to its greater storage in fat led to more inorganic fluoride production in older compared to younger rats. Bone sequestration of inorganic fluoride in younger rats probably accounts for decreased serum inorganic fluoride levels in that group. Both factors cause significant differences in renal exposure to inorganic fluoride; thus the risk of nephrotoxicity is less in younger animals.

FLUORIDE CONCENTRATIONS IN INDUSTRIALIZED BEVERAGES CONSUMED BY CHILDREN IN THE CITY OF BAURU, BRAZIL

PubMed Central

Lodi, Carolina Simonetti; Ramires, Irene; Pessan, Juliano Pelim; Neves, Lucimara Teixeira das; Buzalaf, Marília Afonso Rabelo

2007-01-01

The increasing consumption of juices, soft drinks and teas among children has increased significantly fluoride ingestion at the age range of risk for development of dental fluorosis. Objective: The purpose of this study was to evaluate fluoride concentrations in some brands of industrialized beverages consumed by children in the city of Bauru, SP, Brazil. Material and Methods: 98 brands of beverages were analyzed, divided into 3 lots, comprising 36, 32 and 30 brands, respectively, for the first, second and third lots. Fluoride concentrations were determined by HMDS-facilitated diffusion, using a fluoride ion-specific electrode (Orion 9409). Results: Fluoride concentrations ranged between 0.04 and 1.76 μg F/mL. It was observed a wide variation in fluoride concentrations among the different brands, as well as the different lots of the same brand. There was no information on fluoride concentrations on the labels of any product. Conclusions: Some of the products analyzed could contribute significantly to the total fluoride intake and, thus, be important risk factors for development of dental fluorosis, which indicates the need of controlling the production of these beverages with respect to fluoride concentration. PMID:19089131

The dentist’s role in promoting community water fluoridation

PubMed Central

Melbye, Molly L.R.; Armfield, Jason M.

2013-01-01

Background and Overview Community water fluoridation is an important public health intervention that reduces oral health disparities and increases the health of the population. Promotion of its safety and effectiveness is critical to maintaining its widespread acceptance and ensuring its continued use. Dentists are a potentially important source of knowledge regarding the oral health benefits and safety of water fluoridation. However, few dentists regularly discuss fluorides, and water fluoridation in particular, with patients. The authors aim to describe and discuss the role and importance of dentists’ promotion of public water fluoridation, barriers to dentists’ involvement and some approaches that might influence dentists to promote water fluoridation more actively. Conclusions and Practice Implications Ongoing promotion of fluoridation by dentists is a key factor in ensuring sustained municipal water fluoridation. However, current undergraduate dental curricula do not adequately prepare dentists for this role, and continuing dental education may be insufficient to change clinical practice. Although smoking-cessation literature can shed some light on how to proceed, changing dentists’ practice behavior remains a largely unstudied topic. Dental associations are a key resource for dentists, providing information that can assist them in becoming advocates for water fluoridation. PMID:23283928

[Influence of different concentrations of fluoride in the water on epidemiologic indicators of oral health/disease].

PubMed

de Carvalho, Raquel Baroni; Medeiros, Urubatan Vieira de; dos Santos, Karina Tonini; Pacheco Filho, Antônio Carlos

2011-08-01

The scope of this study was to evaluate access to fluoride sources and oral health hygiene of 237 schoolchildren aged nine to sixteen, from three locations with different fluoride concentrations in the water. The fluoride level in the water of each area was analyzed by the selective electrode technique for the fluoride ion and the prevalence of dental caries and fluorosis were evaluated, respectively, by the DMFT and TSIF index, revealing a statistically significant difference (ANOVA; p <0,05) in the three locations: area without artificial fluoridation (DMTF 5.32 ± 3.49) and 16% of dental fluorosis; area with artificial fluoridation of 0.8 ppmF (DMTF 1.88 ± 2.22) and 94% of dental fluorosis; area with natural fluoridation of 2.54 ppmF (DMTF 3.96 ± 2.38) and 100% of dental fluorosis. The findings suggest that the epidemiologic indicators of oral health/disease are influenced by the presence of fluoride in the water supply and that supervision and orientation are fundamental in the correct use of fluoridated compositions, taking advantage of the maximum benefit in the control of dental caries with minimum risk of the occurrence of dental fluorosis.

Isolation and identification of Trichoderma harzianum from groundwater: An effective biosorbent for defluoridation of groundwater.

PubMed

Koshle, Shalini; Mahesh, S; Swamy, S Nanjunda

2016-01-01

The ability of non-viable form of Trichoderma harzianum, isolated from fluoride rich groundwater, was investigated as biosorbent for defluoridation of groundwater. Biosorption experiments were carried out at laboratory scale for removal of fluoride from groundwater. Significant effect of operational parameters on fluoride biosorption using Trichoderma harzianum as biosorbent was evaluated by varying operational parameters such as: initial fluoride concentration (2-8 mgl(-1)), biosorbent dose (0.4-1.6g/100ml), groundwater pH (6-10), temperature (30-50 degrees C) and biosorption time (30-120 min). The fluoride adsorption isotherms were modeled by Langmuir and Freundlich isotherms. Our result showed that fluoride biosorption, significantly increased with increase in groundwater pH, biosorbent dose, temperature and biosorption time, whereas increase in initial fluoride concentration reduced fluoride removal. The fluoride biosorption was rapid and maximum fluoride uptake was attained with 1.6g 100ml(-1) biosorbent within 60 min. Optimal pH 10 and temperature 50 degrees C gave maximum defluoridation efficiency. Freundlich isotherm fits well for defluoridation of groundwater using Trichoderma harzianum as biosorbent which indicated that biosorbent surface sites were heterogeneous in nature and fitted into heterogeneous site binding model.

Natural fluoride levels in the drinking water, water fluoridation and estimated risk of dental fluorosis in a tropical region of Brazil.

PubMed

Sampaio, Fábio Correia; Silva, Fábia Danielle; Silva, Andréa Cristina; Machado, Ana Thereza; de Araújo, Demétrius Antônio; de Sousa, Erik Melo

2010-01-01

The aim of the present study was to determine the natural fluoride levels in the drinking water supplies of a tropical area of Brazil to identify the cities at risk of high prevalence of dental fluorosis and to provide data for future water fluoridation projects in the region. The present study was carried out in Paraíba, in the north-eastern region of Brazil. A total of 223 cities were selected, and local health workers were instructed to collect three samples of drinking water: one from the main public water supply and the other two from a public or residential tap with the same water source. Fluoride analyses were carried out in duplicate using a fluoride-specific electrode coupled to an ion analyser. A total of 167 cities (75%) provided water samples for analysis. Fluoride levels ranged from 0.1 to 1.0 ppm (mg/l). Samples from most of the cities (n = 163, 73%) presented low levels of fluoride (< 0.5 mg/l). Samples from three cities (a total estimate of 28,222 inhabitants exposed) presented 'optimum' fluoride levels (0.6 to 0.8 mg/l). Samples from one city (16,724 inhabitants) with 1.0 mg/l of fluoride in the water were above the recommended level (0.7 mg/l) for the local temperature. It can be concluded that the cities in this area of Brazil presented low natural fluoride levels in the drinking water and could implement controlled water fluoridation projects when technical requirements are accomplished. A high or a moderate prevalence of dental fluorosis due to the intake of natural fluoride in the drinking water is likely to take place in one city only.

Fluoride gastrointestinal absorption from Na2FPO3/CaCO3- and NaF/SiO2-based toothpastes.

PubMed

Falcão, A; Tenuta, L M A; Cury, J A

2013-01-01

Depending on toothpaste formulation, part of the fluoride is insoluble and would not be totally absorbable in the gastrointestinal tract, thus changing dental fluorosis risk estimation. This hypothesis was tested with formulations with either all fluoride in a soluble form (NaF/SiO2-based toothpaste, 1,100 µg F/g as labeled, 1,129.7 ± 49.4 µg F/g soluble fluoride as analyzed) or with around 20% of insoluble fluoride (Na2FPO3/CaCO3-based toothpaste, 1,450 µg F/g as labeled, 1,122.4 ± 76.4 µg F/g soluble fluoride as analyzed). Toothpastes were evaluated either fresh or after accelerated aging, which increased insoluble fluoride to 40% in the Na2FPO3/CaCO3-based toothpaste. In a blind, crossover clinical trial conducted in five legs, 20 adult volunteers ingested 49.5 µg of total fluoride/kg body weight from each formulation or purified water (control). Whole saliva and urine were collected as bioavailability indicators, and pharmacokinetics parameters calculated showed significantly (p < 0.05) lower fluoride bioavailability for Na2FPO3/CaCO3 toothpaste, which was reduced further after aging. A significant correlation between the amount of soluble fluoride ingested, but not total fluoride, and fluoride bioavailability was found (r = 0.57, p < 0.0001). The findings suggest that the estimated fluorosis risk as a result of ingestion of Na2FPO3/CaCO3-based toothpastes should be calculated based on the toothpaste's soluble rather than total fluoride concentration. Copyright © 2012 S. Karger AG, Basel.

Antibacterial Effect of Silver Diamine Fluoride on Cariogenic Organisms.

PubMed

Lou, Yali; Darvell, Brain W; Botelho, Michael G

2018-05-01

To screen the possible antimicrobial activity of a range of clinically used, silver-based compounds on cariogenic organisms: silver diamine fluoride (SDF), silver fluoride, and silver nitrate. Preliminary screening disk-diffusion susceptibility tests were conducted on Mueller-Hinton agar plates inoculated with Streptococcus mutans, Lactobacillus acidophilus, and Actinomyces naeslundii, organisms known to be cariogenic. In order to identify which component of the silver compounds was responsible for any antibacterial (AB) effect, and to provide controls, the following were also investigated at high and low concentrations: sodium fluoride, ammonium fluoride, ammonium chloride, sodium fluoride, sodium chloride, and sodium nitrate, as well as deionized water as control. A volume of 10 pL of a test solution was dispensed onto a paper disk resting on the inoculated agar surface, and the plate incubated anaerobically at 37°C for 48 hours. The zones of inhibition were then measured. Silver diamine fluoride, silver fluoride, silver nitrate, and ammonium fluoride had significant AB effect (p < 0.05) on all three test organisms, although ammonium fluoride had no effect at low concentration; the remaining other compounds had no effect. Silver ions appear to be the principal AB agent at both high and low concentration; fluoride ions only have an AB effect at high concentration, while ammonium, nitrate, chloride and sodium ions have none. The anticaries effect of topical silver solutions appears restricted to that of the silver ions. Silver compounds, such as SDF, silver fluoride, and silver nitrate have AB effect against cariogenic organisms and these may have clinical impact in arresting or preventing dental decay. Sodium fluoride did not have AB effect under the conditions tested.

A cross-sectional study to assess the intelligence quotient (IQ) of school going children aged 10-12 years in villages of Mysore district, India with different fluoride levels.

PubMed

Sebastian, Shibu Thomas; Sunitha, S

2015-01-01

Besides dental and skeletal fluorosis, excessive fluoride intake can also affect the central nervous system without first causing the physical deformities associated with skeletal fluorosis. With the existence of widespread endemic fluorosis in India, the possible adverse effect of elevated fluoride in drinking water on the Intelligence Quotient (IQ) level of children is a potentially serious public health problem. This study assessed the Intelligence Quotient (IQ) of school going children aged 10-12 years in villages of Mysore district with different fluoride levels. In this cross-sectional study, 405 school children aged 10-12 years were selected from three villages in Mysore district with normal fluoride (1.20 mg F/l), low fluoride (0.40 mg F/l) and high fluoride (2.20 mg F/l) in their water supplies. A pre designed questionnaire was used to collect the required data for the survey which included socio demographic details, oral hygiene practices, diet history, body mass index and dental fluorosis. Intelligence Quotient was assessed using Raven's colored Progressive Matrices Test. In bivariate analysis, significant relationships were found between water fluoride levels and Intelligence Quotient of school children (P < 0.05). In the high fluoride village, the proportion of children with IQ below 90, i.e. below average IQ was larger compared to normal and low fluoride village. Age, gender, parent education level and family income had no significant association with IQ. School children residing in area with higher than normal water fluoride level demonstrated more impaired development of intelligence when compared to school children residing in areas with normal and low water fluoride levels. Thus, children's intelligence can be affected by high water fluoride levels.

Sirtuin1 and autophagy protect cells from fluoride-induced cell stress.

PubMed

Suzuki, Maiko; Bartlett, John D

2014-02-01

Sirtuin1 (SIRT1) is a nicotinamide adenine dinucleotide (NAD(+))-dependent deacetylase functioning in the regulation of metabolism, cell survival and organismal lifespan. Active SIRT1 regulates autophagy during cell stress, including calorie restriction, endoplasmic reticulum (ER) stress and oxidative stress. Previously, we reported that fluoride induces ER-stress in ameloblasts responsible for enamel formation, suggesting that ER-stress plays a role in dental fluorosis. However, the molecular mechanism of how cells respond to fluoride-induced cell stress is unclear. Here, we demonstrate that fluoride activates SIRT1 and initiates autophagy to protect cells from fluoride exposure. Fluoride treatment of ameloblast-derived cells (LS8) significantly increased Sirt1 expression and induced SIRT1 phosphorylation resulting in the augmentation of SIRT1 deacetylase activity. To demonstrate that fluoride exposure initiates autophagy, we characterized the expression of autophagy related genes (Atg); Atg5, Atg7 and Atg8/LC3 and showed that both their transcript and protein levels were significantly increased following fluoride treatment. To confirm that SIRT1 plays a protective role in fluoride toxicity, we used resveratrol (RES) to augment SIRT1 activity in fluoride treated LS8 cells. RES increased autophagy, inhibited apoptosis, and decreased fluoride cytotoxicity. Rats treated with fluoride (0, 50, 100 and 125ppm) in drinking water for 6weeks had significantly elevated expression levels of Sirt1, Atg5, Atg7 and Atg8/LC3 in their maturation stage enamel organs. Increased protein levels of p-SIRT1, ATG5 and ATG8/LC3 were present in fluoride-treated rat maturation stage ameloblasts. Therefore, the SIRT1/autophagy pathway may play a critical role as a protective response to help prevent dental fluorosis. Copyright © 2013 Elsevier B.V. All rights reserved.

The Role of Calcium in Ameliorating the Oxidative Stress of Fluoride in Rats.

PubMed

Mohamed, N E

2016-03-01

The present study was carried out to investigate the effects of fluoride toxicity on some biochemical, hormonal, and histological parameters of female rats and the protective role of calcium against such effects. Adult female albino rats were divided into five groups; control group received distilled water for 60 days, calcium group received calcium carbonate with dose of 50 mg/kg three times per week for 60 days, fluoride group received sodium fluoride with dose of 20 mg/kg three times per week for 60 days, calcium + fluoride group received calcium carbonate (50 mg/kg) then after 2 h received sodium fluoride (20 mg/kg) three times per week for 60 days, and fluoride + calcium group received sodium fluoride (20 mg/kg) three times per week for 30 days then received calcium carbonate (50 mg/kg) three times per week for another 30 days. The results showed that the levels of thiobarbituric acid reactive substances, urea, creatinine, alkaline phosphatase, triiodothyronine, thyroxine, parathormone, phosphorous, magnesium, alanine aminotransferase, aspartate aminotransferase, alkaline phosphatase, and gamma glutamyl transferase were significantly increased in rats treated with fluoride while serum estradiol, calcium, and organ glutathione were significantly decreased. The histological examination of the femur bone revealed that fluoride treatment induced thinning of bone trabeculae with wilding of marrow space, demineralization, and loss of trabeculae interconnections. Also, the histological examination of hepatic and renal tissues of fluoride-treated rats showed some damages in these tissues while administration of calcium carbonate for 30 or 60 days during fluoride treatment minimized such damages. It could be concluded that administration of calcium to female rats can ameliorate the hazardous effects of fluoride observed in the biochemical, hormonal, and histological parameters.

Sirtuin1 and autophagy protect cells from fluoride-induced cell stress

PubMed Central

Suzuki, Maiko; Bartlett, John D.

2014-01-01

Sirtuin1 (SIRT1) is an (NAD+)-dependent deacetylase functioning in the regulation of metabolism, cell survival and organismal lifespan. Active SIRT1 regulates autophagy during cell stress, including calorie restriction, endoplasmic reticulum stress and oxidative stress. Previously, we reported that fluoride induces endoplasmic reticulum (ER) stress in ameloblasts responsible for enamel formation, suggesting that ER-stress plays a role in dental fluorosis. However, the molecular mechanism of how cells respond to fluoride-induced cell stress is unclear. Here, we demonstrate that fluoride activates SIRT1 and initiates autophagy to protect cells from fluoride exposure. Fluoride treatment of ameloblast-derived cells (LS8) significantly increased Sirt1 expression and induced SIRT1 phosphorylation resulting in the augmentation of SIRT1 deacetylase activity. To demonstrate that fluoride exposure initiates autophagy, we characterized the expression of autophagy related genes (Atg); Atg5, Atg7 and Atg8/LC3 and showed that both their transcript and protein levels were significantly increased following fluoride treatment. To confirm that SIRT1 plays a protective role in fluoride toxicity, we used resveratrol (RES) to augmented SIRT1 activity in fluoride treated LS8 cells. RES increased autophagy, inhibited apoptosis, and decreased fluoride cytotoxicity. Rats treated with fluoride (0, 50 and 100 ppm) in drinking water for 6 weeks had significantly elevated expression levels of Sirt1, Atg5, Atg7 and Atg8/LC3 in their maturation stage enamel organs. Increased protein levels of p-SIRT1, ATG5 and ATG8/LC3 were present in fluoride-treated rat maturation stage ameloblasts. Therefore, the SIRT1/autophagy pathway may play a critical role as a protective response to help prevent dental fluorosis. PMID:24296261

Fluoride bioaccumulation and toxic effects on the survival and behavior of the endangered white-clawed crayfish Austropotamobius pallipes (Lereboullet).

PubMed

Aguirre-Sierra, Arantxa; Alonso, Alvaro; Camargo, Julio A

2013-08-01

Laboratory experiments were performed to examine the toxic effects of fluoride (F(-)) on the survival and behavior of white-clawed crayfish (Austropotamobius pallipes). Body fluoride contents (bioaccumulation) of test crayfish were also examined. No significant differences between male and female crayfish regarding mortality, escape (tail-flip) response, and fluoride bioaccumulation were detected. For mortality, 48-, 72-, 96-, 120-, 144-, 168-, and 192-h median lethal concentrations (LC50) were estimated to be 93.0, 55.3, 42.7, 36.5, 32.9, 30.6, and 28.9 mg F(-)/l, respectively. For the escape response, 48-, 72-, 96-, 120-, 144-, 168- and 192-h median effective concentrations (EC50) were estimated to be 18.4, 11.1, 8.6, 7.4, 6.7, 6.2 and 5.9 mg F(-)/l, respectively. Average food consumption in test crayfish tended to decrease with increasing water fluoride concentration with a 192-h lowest-observed effect concentration of 10.7 mg F(-)/l. These results indicate that the escape response was the most sensitive end point to fluoride toxicity followed by food consumption and mortality. Fluoride bioaccumulation in test crayfish increased with increasing water fluoride concentration and exposure time. The exoskeleton accumulated more fluoride than muscle. A comparison of the obtained results with previous data for other freshwater invertebrates shows that white-clawed crayfish are relatively tolerant to fluoride toxicity. We conclude that fluoride pollution in freshwater ecosystems should not be viewed as an important risk factor contributing to the catastrophic decrease of A. pallipes in many European countries. Our results indicate that fluoride bioaccumulation in A. pallipes might be used as a bioindicator of fluoride pollution in freshwater ecosystems where it is present.

Sub-chronic exposure to fluoride impacts the response to a subsequent nephrotoxic treatment with gentamicin.

PubMed

Cárdenas-González, Mariana; Jacobo Estrada, Tania; Rodríguez-Muñoz, Rafael; Barrera-Chimal, Jonatan; Bobadilla, Norma A; Barbier, Olivier C; Del Razo, Luz M

2016-02-01

Fluoride is an important groundwater contaminant, and more than 200 million people are exposed to high fluoride levels in drinking water, the major source of fluoride exposure. Exposure above 2 ppm of fluoride is associated with renal impairment in humans. In rats, moderate levels of fluoride induce kidney injury at early stages in which the glomerular filtration rate (GFR) is not altered. In the present study, we investigated if sub-nephrotoxic stimulus induced by fluoride might impact the response to a subsequent nephrotoxic treatment with gentamicin. Male Wistar rats (~21 days) were exposed to 0, 15 or 50 ppm of fluoride through drinking water during 40 days. Afer that, rats were co-exposed to gentamicin (40 mg kg(-1) day(-1), 7 days). Gentamicin induced a marked decrease in the GFR and an increase in urinary levels as well as the protein and mRNA expression of biomarkers of early kidney injury, such as Kim-1. Interestingly, gentamicin nephrotoxicity was less pronounced in groups previously exposed to fluoride than in the group only treated with gentamicin. Fluoride induced Hsp72, a cytoprotective molecule, which might have improved the response against gentamicin. Moreover, fluoride decreased the expression of megalin, a molecule necessary for internalization of gentamicin into the proximal tubule, potentially reducing gentamicin accumulation. The present results suggest that fluoride reduced gentamicin-induced nephrotoxicity by inducing a compensatory response carried out by Hsp72 and by decreasing gentamicin accumulation. These findings should not be interpreted to suggest that fluoride is a protective agent as megalin deficiency could lead to serious adverse effects on the kidney physiology. Copyright © 2015 John Wiley & Sons, Ltd.

Effect of long-term exposure to fluoride in drinking water on risks of bone fractures.

PubMed

Li, Y; Liang, C; Slemenda, C W; Ji, R; Sun, S; Cao, J; Emsley, C L; Ma, F; Wu, Y; Ying, P; Zhang, Y; Gao, S; Zhang, W; Katz, B P; Niu, S; Cao, S; Johnston, C C

2001-05-01

Findings on the risk of bone fractures associated with long-term fluoride exposure from drinking water have been contradictory. The purpose of this study was to determine the prevalence of bone fracture, including hip fracture, in six Chinese populations with water fluoride concentrations ranging from 0.25 to 7.97 parts per million (ppm). A total of 8266 male and female subjects > or =50 years of age were enrolled. Parameters evaluated included fluoride exposure, prevalence of bone fractures, demographics, medical history, physical activity, cigarette smoking, and alcohol consumption. The results confirmed that drinking water was the only major source of fluoride exposure in the study populations. A U-shaped pattern was detected for the relationship between the prevalence of bone fracture and water fluoride level. The prevalence of overall bone fracture was lowest in the population of 1.00-1.06 ppm fluoride in drinking water, which was significantly lower (p < 0.05) than that of the groups exposed to water fluoride levels > or =4.32 and < or =0.34 ppm. The prevalence of hip fractures was highest in the group with the highest water fluoride (4.32-7.97 ppm). The value is significantly higher than the population with 1.00-1.06 ppm water fluoride, which had the lowest prevalence rate. It is concluded that long-term fluoride exposure from drinking water containing > or =4.32 ppm increases the risk of overall fractures as well as hip fractures. Water fluoride levels at 1.00-1.06 ppm decrease the risk of overall fractures relative to negligible fluoride in water; however, there does not appear to be similar protective benefits for the risk of hip fractures.

Hospitalizations for dental infections: optimally versus nonoptimally fluoridated areas in Israel.

PubMed

Klivitsky, Amir; Tasher, Diana; Stein, Michal; Gavron, Etan; Somekh, Eli

2015-03-01

Odontogenic infections may result in local, systemic, and even potentially life-threatening complications. The authors investigated whether water fluoridation was associated with reduction in rates of hospitalizations due to odontogenic infections. The authors included cities in Israel that had fluoride concentrations of either 0.7 milligrams per liter or more (optimally fluoridated) or 0.5 mg/L or less (nonoptimally fluoridated) and that had a public water fluoride concentration consistent for the last decade. The authors compared hospitalization rates (per 10,000 children) for odontogenic infections in children younger than 18 years in each socioeconomic group between optimally and nonoptimally fluoridated cities. The authors included 1,413 hospitalizations between January 2005 and December 2011 of children residing in the 38 studied municipalities. The cities with the higher fluoride concentration reported a lower hospitalization rate (2.0 versus 4.3 for cities with a lower fluoride concentration; relative risk [RR]: 2.16; P < .001). When the authors divided cities into 3 socioeconomic groups, a large difference in hospitalization rates was seen in the lowest socioeconomic group (10.1 versus 2.6; RR: 3.79; P < .001) and the middle socioeconomic group (3.6 versus 1.9; RR: 2.35; P < .001) in optimally and nonoptimally fluoridated cities, respectively. No significant difference in hospitalization rates was apparent between the 2 fluoridation groups in the higher socioeconomic level. These results clearly indicate that there is an association between adequacy of water fluoridation and hospitalization due to dental infections among children and adolescents. This effect is more prominent in populations of lower socioeconomic status. Water fluoridation is associated with reduction in dental health disparity. Copyright © 2015 American Dental Association. Published by Elsevier Inc. All rights reserved.

Keep Your Mouth Healthy: Oral Care for Older Adults

MedlinePlus

... decay and gum disease by brushing daily with fluoride toothpaste and flossing. Also visit the dentist regularly ... Your Mouth Healthy Drink fluoridated water and use fluoride toothpaste. Fluoride protects against dental decay at all ...

Time-Resolved Infrared Reflectance Studies of the Dehydration-Induced Transformation of Uranyl Nitrate Hexahydrate to the Trihydrate Form

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

Johnson, Timothy J.; Sweet, Lucas E.; Meier, David E.

Uranyl nitrate is a key species in the nuclear fuel cycle. However, this species is known to exist in different states of hydration, including the hexahydrate ([UO2(NO3)2(H2O)6] often called UNH), the trihydrate [UO2(NO3)2(H2O)3 or UNT], and in very dry environments the dihydrate form [UO2(NO3)2(H2O)2]. Their relative stabilities depend on both water vapor pressure and temperature. In the 1950s and 1960s the different phases were studied by infrared transmission spectroscopy, but were limited both by instrumental resolution and by the ability to prepare the samples for transmission. We have revisited this problem using time-resolved reflectance spectroscopy, which requires no sample preparationmore » and allows dynamic analysis while the sample is exposed to a flow of N2 gas. Samples of known hydration state were prepared and confirmed via X-ray diffraction patterns of known species. In reflectance mode the hexahydrate UO2(NO3)2(H2O)6 has a distinct uranyl asymmetric stretch band at 949.0 cm-1 that shifts to shorter wavelengths and broadens as the sample desiccates and recrystallizes to the trihydrate, first as a shoulder growing in on the blue edge but ultimately results in a doublet band with reflectance peaks at 966 and 957 cm-1. The data are consistent with transformation from UNH to UNT as UNT has two inequivalent UO22+ sites. The dehydration of UO2(NO3)2(H2O)6 to UO2(NO3)2(H2O)3 is both a structural and morphological change that has the lustrous lime green UO2(NO3)2(H2O)6 crystals changing to the matte greenish yellow of the trihydrate solid. The phase transformation and crystal structures were confirmed by density functional theory calculations and optical microscopy methods, both of which showed a transformation with two distinct sites for the uranyl cation in the trihydrate, with but one in the hexahydrate.« less

In situ ligand synthesis with the UO{sub 2}{sup 2+} cation under hydrothermal conditions

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

Frisch, Mark; Cahill, Christopher L.; Geophysical Laboratory, Carnegie Institution of Washington, Washington, DC

A novel uranium (VI) coordination polymer, (UO{sub 2}){sub 2}(C{sub 2}O{sub 4})(C{sub 5}H{sub 6}NO{sub 3}){sub 2} (1), has been prepared under the hydrothermal reaction of uranium nitrate hexahydrate and L-pyroglutamic acid. Compound 1 (monoclinic, C2/c, a=22.541(6) A, b=5.7428(15) A, c=15.815(4) A, {beta}=119.112(4){sup o}, Z=4, R{sub 1}=0.0237, wR{sub 2}=0.0367) consists of uranium pentagonal bipyramids linked via L-pyroglutamate and oxalate anions to form an overall two-dimensional (2D) structure. With the absence of oxalic acid within the starting materials, the oxalate anions are hypothesized to form in situ whereby decarboxylation of L-pyroglutamic acid occurs followed by coupling of CO{sub 2} to form the oxalatemore » linkages as observed in the crystal structure. Addition of copper (II) to this system appears to promote oxalate formation in that synthetic moolooite (Cu(C{sub 2}O{sub 4}).nH{sub 2}O; 0{<=}n{<=}1) and a known uranyl oxalate [(UO{sub 2}){sub 2}(C{sub 2}O{sub 4})(OH){sub 2}(H{sub 2}O){sub 2}.H{sub 2}O], co-crystallize in significant quantity. Compound 1 exhibits the characteristic uranyl emission spectrum upon either direct uranyl excitation or ligand excitation, the latter of which shows an increase in relative intensity. This subsequent increase in the intensity indicates an energy transfer from the ligand to the uranyl cations thus illustrating an example of the antenna effect in the solid state. - Graphical abstract: A novel homometallic coordination polymer (UO{sub 2}){sub 2}(C{sub 2}O{sub 4})(C{sub 5}H{sub 6}NO{sub 3}){sub 2}, in the uranium-L-pyroglutamic acid system has been synthesized under hydrothermal conditions. The title compound consists of uranium pentagonal bipyramids bridged through both L-pyroglutamate and oxalate linkages to produce a 3D crystal structure. The oxalate anions are theorized to result from decarboxylation of L-pyroglutamic acid followed by subsequent coupling of CO{sub 2}.« less

Uranyl Coordination Polymers Incorporating η5-Cyclopentadienyliron-Functionalized η6-Phthalate Metalloligands: Syntheses, Structures and Photophysical Properties

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

Kerr, Andrew T.; Kumalah, Sayon A.; Holman, K. T.

2013-10-06

The reaction of two η5-cyclopentadienyliron(II)-functionalized terephthalate and phthalate metalloligands, namely [(η5-C5H5)FeII(η6-1,4-HO2CC6H4CO2H)][(η5-C5H5)FeII(η6-1,4-HO2CC6H4CO2)][PF6] and [(η5-C5H5)FeII(η6-1,2-HO2CC6H4CO2H)][(η5-C5H5)FeII(η6-1,2-HO2CC6H4CO2)][PF6]—hereafter [H2 CpFeTP][HCpFeTP][PF6] and [H2 CpFeP][HCpFeP][PF6], respectively—with [UO2(NO3)2]·6H2O under hydrothermal conditions yielded four new coordination polymers; (1) [(UO2)F(HCpFeTP)(PO4H2)]·2H2O, (2) [(UO2)2(CpFeTP)4]·5H2O, (3) [(UO2)2F3(H2O)(CpFeP)], and (4) [H2 CpFeP][UO2F3]. The use of metalloligands has proven to be a viable route towards the incorporation of a secondary metal center into uranyl bearing materials. Depending upon the protonation state, the iron sandwich metalloligands may vary from zwitterionic neutral or monoanionic coordinating species as observed in compounds 1–3, or a positively charged species that hydrogen bonds with anionic [UO2F3]- chains as observed in 4.more » Further, the hydrolysis of the charge balancing PF6 - anion increases the diversity of UO2 2+ coordinating species by contributing both F- and PO4 3- anions (1, 3, 4). The luminescent properties of 1–4 were also studied and revealed the absence of uranyl emission, suggestive of a possible energy transfer from the uranyl cation to the iron(II) metal center.« less

Time-resolved infrared reflectance studies of the dehydration-induced transformation of uranyl nitrate hexahydrate to the trihydrate form

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

Johnson, Timothy J.; Sweet, Lucas E.; Meier, David E.

2015-09-08

Uranyl nitrate is a key species in the nuclear fuel cycle. However, this species is known to exist in different states of hydration, including the hexahydrate ([UO 2(NO 3) 2(H 2O) 6] often called UNH), the trihydrate [UO 2(NO 3) 2(H 2O) 3 or UNT], and in very dry environments the dihydrate form [UO 2(NO 3) 2(H 2O) 2]. Their relative stabilities depend on both water vapor pressure and temperature. In the 1950s and 1960s, the different phases were studied by infrared transmission spectroscopy but were limited both by instrumental resolution and by the ability to prepare the samples formore » transmission. We have revisited this problem using time-resolved reflectance spectroscopy, which requires no sample preparation and allows dynamic analysis while the sample is exposed to a flow of N 2 gas. Samples of known hydration state were prepared and confirmed via X-ray diffraction patterns of known species. In reflectance mode the hexahydrate UO 2(NO 3) 2(H 2O) 6 has a distinct uranyl asymmetric stretch band at 949.0 cm –1 that shifts to shorter wavelengths and broadens as the sample desiccates and recrystallizes to the trihydrate, first as a shoulder growing in on the blue edge but ultimately results in a doublet band with reflectance peaks at 966 and 957 cm –1. The data are consistent with transformation from UNH to UNT as UNT has two inequivalent UO 2 2+ sites. The dehydration of UO 2(NO 3) 2(H 2O) 6 to UO 2(NO 3) 2(H 2O) 3 is both a structural and morphological change that has the lustrous lime green UO 2(NO 3) 2(H 2O) 6 crystals changing to the matte greenish yellow of the trihydrate solid. As a result, the phase transformation and crystal structures were confirmed by density functional theory calculations and optical microscopy methods, both of which showed a transformation with two distinct sites for the uranyl cation in the trihydrate, with only one in the hexahydrate.« less

Electrospray ionization of uranyl-citrate complexes

NASA Astrophysics Data System (ADS)

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 and charge state distributions.

Hydrothermal syntheses, structures, and properties of the new uranyl selenites Ag(2)(UO(2))(SeO(3))(2), M[(UO(2))(HSeO(3))(SeO(3))] (M = K, Rb, Cs, Tl), and Pb(UO(2))(SeO(3))(2).

PubMed

Almond, Philip M; Albrecht-Schmitt, Thomas E

2002-03-11

The transition metal, alkali metal, and main group uranyl selenites, Ag(2)(UO(2))(SeO(3))(2) (1), K[(UO(2))(HSeO(3))(SeO(3))] (2), Rb[(UO(2))(HSeO(3))(SeO(3))] (3), Cs[(UO(2))(HSeO(3))(SeO(3))] (4), Tl[(UO(2))(HSeO(3))(SeO(3))] (5), and Pb(UO(2))(SeO(3))(2) (6), have been prepared from the hydrothermal reactions of AgNO(3), KCl, RbCl, CsCl, TlCl, or Pb(NO(3))(2) with UO(3) and SeO(2) at 180 degrees C for 3 d. The structures of 1-5 contain similar [(UO(2))(SeO(3))(2)](2-) sheets constructed from pentagonal bipyramidal UO(7) units that are joined by bridging SeO(3)(2-) anions. In 1, the selenite oxo ligands that are not utilized within the layers coordinate the Ag(+) cations to create a three-dimensional network structure. In 2-5, half of the selenite ligands are monoprotonated to yield a layer composition of [(UO(2))(HSeO(3))(SeO(3))](1-), and coordination of the K(+), Rb(+), Cs(+), and Tl(+) cations occurs through long ionic contacts. The structure of 6 contains a uranyl selenite layered substructure that differs substantially from those in 1-5 because the selenite anions adopt both bridging and chelating binding modes to the uranyl centers. Furthermore, the Pb(2+) cations form strong covalent bonds with these anions creating a three-dimensional framework. These cations occur as distorted square pyramidal PbO(5) units with stereochemically active lone pairs of electrons. These polyhedra align along the c-axis to create a polar structure. Second-harmonic generation (SHG) measurements revealed a response of 5x alpha-quartz for 6. The diffuse reflectance spectrum of 6 shows optical transitions at 330 and 440 nm. The trailing off of the 440 nm transition to longer wavelengths is responsible for the orange coloration of 6.

Effect of fluoride ion on the stability of DNA hairpin

NASA Astrophysics Data System (ADS)

Liu, Chao; Zhai, Weili; Gong, Hongling; Liu, Yanhui; Chen, Hu

2017-06-01

Fluoride prevents tooth decay as an additive in oral hygiene products, while high dose intake of fluoride from contaminated drinking water leads to fluorosis. Here we studied the effect of fluoride ion on the stability of DNA double helix using magnetic tweezers. The equilibrium critical force decreases with increasing concentration of fluoride in the range from 1 mM to 100 mM. Our results give the first quantitative measurement of DNA stability in the presence of fluoride ion, which might disturb DNA-related biological processes to cause fluorosis.

PROCESS FOR THE PRODUCTION OF AMMONIUM URANIUM FLUORIDE

DOEpatents

Ellis, A.S.; Mooney, R.B.

1953-08-25

This patent relates to the preparation of ammonium uranium fluoride. The process comprises adding a water soluble fluoride to an aqueous solution of a uranous compound containing an ammonium salt, and isolating the resulting precipitate. This patent relates to the manufacture of uranium tetnafluoride from ammonium uranium fluoride, NH/sub 4/UF/sub 5/. Uranium tetrafluoride is prepared by heating the ammonium uranium fluoride to a temperature at which dissociation occurs with liberation of ammonium fluoride. Preferably the process is carried out under reduced pressure, or in a current of an inert gas.

Improving Dental Health of DOD Related Persons Assigned to Okinawa by Using Fluoridated Salt in Lieu of Water Fluoridation: A Comparative Analysis

DTIC Science & Technology

1999-04-01

1994-1997). During this time, the 18th Medical Group (MDG) set fluoridating the base water supply as a goal to prevent dental caries – a noble and...related personnel. Supplemental fluoride may be an effective method of improving oral health by reducing dental caries . Water and salt fluoridation ...372-5,381. 9 Colonel Canning and Mr. Noorda, “Talking Paper on Fluoridation of Kadena AB Drinking Water ,” 26 Apr 1995. 5 Chapter 2 Dental Caries The

[Influence of natural fluoride concentration in drinking water on dental health of first class pupils in an area with enhanced fluoride content at the beginning of the 21st century].

PubMed

Steinmeyer, R

2011-08-01

Since the end of the first half of the 20 (th) century it is well-known that fluoride concentrations in drinking water of about 1 ppm reduce the prevalence of dental caries by about 40-60%. This knowledge led to the fluoridation of drinking water during the second half of the 20 (th) century in many countries, including East Germany. Although the natural F (-) content in drinking water in Germany is usually very low, the eastern Eifel is one of the few larger areas in Germany with (nearly) optimal (0.7-1.0 ppm) or moderately enhanced (0.3-0.7 ppm) natural fluoride concentrations in drinking water. 30 years ago, in 1977, the caries prevalence of children of various age groups in the fluoride-rich areas of the eastern Eifel was established by Einwag to be about 40% lower than in adjacent fluoride-poor regions (0.1 ppm). Meanwhile fluoride has become available from many different sources for children of any age: e. g., toothpaste (with 500 ppm fluoride even for very young children who just got the first tooth), fluoridated salt, professional fluoride applications (paid by health insurances), the rising consumption of mineral waters (many of which have a fluoride content >0.3 ppm). This poses the question of the current influence of enhanced natural drinking water fluoride concentrations on caries prevalence in children. The results of the dental examinations of 9 555 pupils (6 or 7 years old) of the first classes of all 63 primary schools in the Landkreis Mayen-Koblenz from 5 years (2004/2005-2008/2009) are compared to the fluoride content of the drinking water. The data show no obvious correlation between dental health and fluoride concentration for any of the dental health parameters investigated. However, in spite of the low geographic resolution of social parameters, there was a notable connection between dental health status and sociodemographic indicators for the respective region. 30 years after the study by Einwag in the same region, the natural fluoride content of drinking water either had no influence on dental health at all, or this influence is so diminutive that it is exceeded by far by sociodemographic factors. Obviously there is much more fluoride available from other sources nowadays compared to 30 years ago. The results may also have implications for the administration of fluoride tablets and support the recommendations of the DGZMK (Deutsche Gesellschaft für Zahn-, Mund- und Kieferheilkunde) from the year 2000, restricting the administration of fluoride tablets to special situations following an individual anamnesis of fluoride uptake. © Georg Thieme Verlag KG Stuttgart · New York.

Fluoride release, recharge and mechanical property stability of various fluoride-containing resin composites.

PubMed

Naoum, S; Ellakwa, A; Martin, F; Swain, M

2011-01-01

To determine the fluoride release and recharge of three fluoride-containing resin composites when aged in deionized water (pH 6.5) and lactic acid (pH 4.0) and to assess mechanical properties of these composites following aging. Three fluoride-containing resin composites were analyzed in this study; a new giomer material named Beautifil II, Gradia Direct X, and Tetric EvoCeram. A glass ionomer cement, Fuji IX Extra, was also analyzed for comparison. Specimens were fabricated for two test groups: group 1 included 10 disc specimens initially aged 43 days in deionized water (five specimens) and lactic acid (five specimens). The fluoride release from these specimens was measured using a fluoride-specific electrode on nine specific test days during the aging period. Following 49 days of aging, each specimen was recharged in 5000 ppm neutral sodium fluoride solution for 5 minutes. Specimen recharge was then repeated on a weekly basis for 3 weeks. The subsequent fluoride rerelease was measured at 1, 3, and 7 days after each recharge episode. Group 2 included six disc specimens aged for 3 months in deionized water (three specimens) and lactic acid (three specimens). The hardness and elastic modulus of each specimen was measured using nano-indentation at intervals of 24 hours, 1 month, and 3 months after fabrication. Two-way factorial analysis of variance (ANOVA) and post-hoc (Tukey) testing was used to assess the influence of storage media (two levels) and composite type (three levels) on the fluoride release, fluoride rerelease, hardness, and elastic modulus of the assessed materials. The level of significance was set at p=0.05. All three composites demonstrated fluoride release and recharge when aged in both deionized water and lactic acid. The cumulative fluoride released from Beautifil II into both media was substantially greater than the fluoride released from Gradia Direct X and Tetric EvoCeram after 43 days aging and was significantly (p<0.05, ANOVA, Tukey test) greater during several analysis periods. Beautifil II demonstrated the greatest recharge ability of the three composites over the 3-week recharge period in both media. Fuji IX Extra demonstrated a significantly (p<0.05) greater fluoride release and recharge compared with the three resin composites. The elastic modulus and hardness of the three composites did not decrease significantly (p<0.05) with fluoride release or fluid uptake over the 3-month aging period, in either media. The three composites in the present study demonstrated fluoride release (Beautiful II > Gradia Direct X > Tetric EvoCeram) and fluoride recharge (Beautiful II > Gradia Direct X > Tetric EvoCeram). This capability raises the possibility of fluoride-containing composites exhibiting a lower incidence of recurrent caries than non fluoride–containing composites. The mechanical properties of each composite did not diminish with aging and fluoride release over the testing period.

Evaluation and comparison of quantity and pattern of fluoride release from orthodontic adhesives: an in vitro study.

PubMed

Regalla, Ravindra Reddy; Jadav, Chandulal; Babu, Devatha Ashok; Sriram, Roopa Rani S; Sriram, Sanjay Krishna; Kattimani, Vivekanand S

2014-01-01

Orthodontic treatment has gained popularity since beginning of era of dentistry. Now a day, everyone is conscious about their appearance, smile and function. During orthodontic treatment use of brackets and adhesives are common. The bonding of brackets will cause demineralization which requires the fluoridation. So the study has been under- taken to analyze the pattern of fluoride release by commercially available adhesive bonding material for the prevention of demineralization. To evaluate and compare the clinical significance of quantity and pattern of fluoride release from three commercially available adhesives. To assess the pattern of fluoride release and quantity, to reduce the decalcification of enamel around orthodontic brackets and bands during treatment and to prevent further use of topical fluoride both office and self-use agents for prevention of demineralization/for remineralization. The comparison of quantity and pattern of fluoride release study involved commercially available bonding adhesives. They are: Group I--resin reinforced glass Ionomer light cure material (OrthoLC), Group II--fluoride releasing composite resin material (Excel) and Group III--conventional composite (Relay-a-bond) evaluated on 78 freshly extracted premolar teeth divided into three groups consisting 26 specimens in each group. The prepared specimens were stored in artificial saliva at 37°C in an incubator for subsequent fluoride analysis using ORION ion selective electrode coupled with ionalyzer 901. Fluoride analysis made at 24 hours intervals for first 3 consecutive days and thereafter at the end of 10th, 17th, 24th and 31st day of bonding. The data obtained were tabulated and interpreted by statistical analysis using 't' test and one-way analysis of variance (ANOVA). The quantity of fluoride release in groups I and II was significant even at the end of 31st day. The one-way AVOVA showed intra and inter group significance in the quantity of fluoride release. But group III with zero fluoride release with significant decalcification on enamel which requires external use of topical fluorides. The pattern of fluoride released was 3.06 ppm for group I and 2.01 ppm for group II and was declined sharply after 24 hours; and continued to decline in subsequent weeks. Mean quantity of fluoride release by group I was 15.08 ppm were as group II was 9.02 ppm over the test period of 31 days. At the end of 31st day the group I bonding adhesive was releasing considerable amount of fluoride compared to group II whereas group III was nil. At all the periods inter and intra group mean values were highly significant. And group III acted as base line or control group as it was non-fluoride releasing material. Both the fluoride releasing adhesive bond material are useful to reduce the risk of demineralization and further prevent the usage of topical fluoride application and reduce cost and clinical visiting time for both patient and clinician.

A 4-year assessment of a new water-fluoridation scheme in New South Wales, Australia.

PubMed

Blinkhorn, Anthony S; Byun, Roy; Mehta, Pathik; Kay, Meredith

2015-06-01

To monitor the changes in dental caries prevalence of 5- to 7-year-old children living in a fluoridated area, a newly fluoridated area and in an area without water fluoridation, in NSW, Australia. Dental caries prevalence was recorded for 5- to 7-year-old children, living in the three study locations, by six trained and calibrated examiners in 2008, 2010 and 2012. A questionnaire recorded demographic data, toothbrushing behaviour and sugary drink consumption. Caries experience was measured using the decayed, missing, and filled teeth (dmft) index for primary teeth, the percentage of children who were caries free and the significant caries index. Univariate analysis was undertaken to determine independent predictors of caries. The caries prevalence changed over time. In 2008, the mean dmft index was 1.40 for the fluoridated area, 2.02 for the area about to fluoridate and 2.09 for the unfluoridated control. By 2012, these mean dmft scores were 0.69, 0.72 and 1.21, respectively. In the two areas where children received fluoridated water, the significant caries index was 2.30 for the fluoridated area and 2.40 for the newly fluoridated area. The significant caries score for children in the unfluoridated location was 3.93. Multivariate analysis showed that over time the differences in dental caries prevalence between the established fluoride area and the newly fluoridated area diminished. However, children in the unfluoridated control area continued to demonstrate significant differences in the mean number of decayed teeth compared with children in the fluoridated comparator sites, and the proportions of children free from decay were significantly higher in the fluoridated areas than in the unfluoridated area. Fluoridation of public water supplies in Gosford and Wyong offers young children better dental health than those children who do not have access to this public health measure. © 2015 FDI World Dental Federation.

Prevalence of dental caries and dental fluorosis among 12 and 15 years old school children in relation to fluoride concentration in drinking water in an endemic fluoride belt of Andhra Pradesh.

PubMed

Shekar, Chandra; Cheluvaiah, Manjunath Bhadravathi; Namile, Dinesh

2012-01-01

The published literature on the prevalence and severity of dental caries and dental fluorosis among school going children in Nalgonda district - An Endemic Fluoride belt was lacking . To assess the prevalence and severity of dental fluorosis and dental caries among 12 and 15 years old children in relation to fluoride concentration in drinking water . It was a cross-sectional study, done in Nalgonda district of Andhra Pradesh, India (endemic fluoride belt) . 5 of the 59 mandals in the district of Nalgonda were selected by simple random sampling. Then, 3 schools from each of these selected mandals were chosen at random. All the eligible 6 th and 9 th standard children were considered for final analysis. The demographic and other relevant information was collected by 3 trained and calibrated dentists, using a structured questionnaire. Dental caries were recorded using dentition status and treatment needs and fluorosis were recorded by Dean's fluorosis index. The statistical analysis was done using SPSS version 16. The prevalence of dental caries among children was 56.3% with the highest in below optimal fluoride area (71.3%) and lowest in optimal fluoride area (24.3%). The prevalence of dental fluorosis was 71.5%. The prevalence was 39.7% in below optimal fluoride area and 100% in high and very fluoride areas. The prevalence and severity of fluorosis increased with increasing fluoride concentration. The caries experience was more among boys than girls. There was a negative correlation between dental caries and fluoride concentration for the entire study population. However, in high fluoride areas, there was a positive correlation between fluoride concentration and dental caries. Water defluoridation on an urgent basis is a priority here than water fluoridation, because the prevalence and severity of dental flurorosis is very high.

Associations between fluorosis of permanent incisors and fluoride intake from infant formula, other dietary sources and dentifrice during early childhood

PubMed Central

Levy, Steven M.; Broffitt, Barbara; Marshall, Teresa A.; Eichenberger-Gilmore, Julie M.; Warren, John J.

2017-01-01

Objectives The authors describe associations between dental fluorosis and fluoride intakes, with an emphasis on intake from fluoride in infant formula. Methods The authors administered periodic questionnaires to parents to assess early fluoride intake sources from beverages, selected foods, dentifrice and supplements. They assessed relationships between fluorosis of the permanent maxillary incisors and fluoride intake from beverages and other sources, both for individual time points and cumulatively using area-under-the-curve (AUC) estimates. The authors determined effects associated with fluoride in reconstituted powdered infant formulas, along with risks associated with intake of fluoride from dentifrice and other sources. Results Considering only fluoride intake from age 3 to 9 months, the authors found that participants with fluorosis (97 percent of which was mild) had significantly greater cumulative fluoride intake (AUC) from reconstituted powdered infant formula, other beverages with added water or a combination of these than did those without fluorosis. For participants aged 16 to 36 months, participants with fluorosis had significantly higher fluoride intake from water by itself, dentifrice or a combination of these than did those without fluorosis. In a model combining both the 3- to 9-month and 16- to 36-months age groups, the significant variables were fluoride intake from reconstituted powder concentrate formula (by participants aged 3–9 months), other beverages with added water (also by participants aged 3–9 months) and dentifrice (by participants aged 16–36 months). Conclusions Greater fluoride intakes from reconstituted powdered formulas (when participants were aged 3–9 months) and other water-added beverages (when participants were aged 3–9 months) increased fluorosis risk as did higher dentifrice intake by participants when aged 16 to 36 months. Clinical Implications Results suggest that prevalence of mild dental fluorosis could be reduced by avoiding ingestion of large quantities of fluoride from reconstituted powdered concentrate infant formula and fluoridated dentifrice. PMID:20884921

Fluoride releasing and enamel demineralization around orthodontic brackets by fluoride-releasing composite containing nanoparticles.

PubMed

Melo, Mary A S; Morais, Weslanny A; Passos, Vanara F; Lima, Juliana P M; Rodrigues, Lidiany K A

2014-05-01

Fluoride-containing materials have been suggested to control enamel demineralization around orthodontic brackets during the treatment with fixed appliances. The improvement of their properties has been made through innovations, such as the application of nanotechnology by incorporation of nanofillers. This in vitro study evaluated the capacity of fluoride releasing and enamel demineralization inhibition of fluoride-releasing nanofilled cement around orthodontic brackets using an artificial caries biofilm model. Forty bovine enamel discs were selected by evaluating surface microhardness and randomized into four groups (n = 10): non-fluoride-releasing microfilled composite, fluoride-releasing microfilled composite, resin-modified glass ionomer cement (RMGI), and fluoride-releasing nanofilled composite (FN). After brackets bonding in each disc, the specimens were subjected to a cariogenic challenge through a Streptococcus mutans biofilm model. After the experimental period, the biofilm formed around the brackets was collected for fluoride analysis and the mineral loss around the brackets was determined by integrated demineralization via cross-sectional microhardness measurement at 20 and 70 μm from the bracket margin. Additionally, samples of each group were subjected to energy-dispersive X-ray spectroscopy (EDX) analysis examined under a scanning electron microscopy (SEM). ANOVA followed by Tukey test were applied for fluoride concentration and mineral loss data, respectively. At both distances, only RMGI statistically differed from the other groups presenting the lowest demineralization, although there was a trend to a lower demineralization of enamel around brackets in FN group. Similar condition was found to fluoride concentration and EDX/SEM analysis. Under the cariogenic exposure condition of this study, the fluoride-releasing nanofilled material had similar performance to fluoride-releasing microfilled materials. The presence of nanofillers in the fluoride-releasing materials studied did not promote further benefits against caries lesion development around brackets and presented inferior demineralization inhibition than the resin-modified glass ionomer material.

Performance of novel hydroxyapatite nanowires in treatment of fluoride contaminated water.

PubMed

He, Junyong; Zhang, Kaisheng; Wu, Shibiao; Cai, Xingguo; Chen, Kai; Li, Yulian; Sun, Bai; Jia, Yong; Meng, Fanli; Jin, Zhen; Kong, Lingtao; Liu, Jinhuai

2016-02-13

Novel ultralong hydroxyapatite (HAP) nanowires were successfully prepared for fluoride removal for the first time. The fluoride adsorption on the HAP nanowires was studied on a batch mode. The results revealed that the adsorption data could be well described by the Freundlich model, and the adsorption kinetic followed the pseudo-second-order model. The maximum of adsorption capacity was 40.65 mg/g at pH 7.0 when the fluoride concentration is 200mg/L. The thermodynamic parameters suggested that the adsorption of fluoride was a spontaneous endothermic process. The FT-IR, XPS and Zeta potential analysis revealed that both anion exchange and electrostatic interactions were involved in the adsorption of fluoride. Furthermore, the HAP nanowires were made into HAP membrane through a simple process of suction filtration. Membrane filtration experiments revealed that the fluoride removal capabilities depended on the membrane thickness, flow rate and initial concentration of fluoride. The as-prepared membrane could remove fluoride efficiently through continues filtration. The filtered water amount could reach 350, 192, and 64 L/m(2) when the fluoride concentrations were 4, 5 and 8 ppm, respectively, using the HAP membrane with only 150 μm thickness. The as-synthesized ultralong HAP nanowires were thus demonstrated to be very effective and biocompatible adsorbents for fluoride removal from contaminated water. Copyright © 2015 Elsevier B.V. All rights reserved.