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

Sorption mechanisms of metals to graphene oxide

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

Showalter, Allison R.; Duster, Thomas A.; Szymanowski, Jennifer E. S.

2016-05-01

Environmental toxic metal contamination remediation and prevention is an ongoing issue. Graphene oxide is highly sorptive for many heavy metals over a wide pH range under different ionic strength conditions. We present x-ray absorption fine structure (XAFS) spectroscopy results investigating the binding environment of Pb(II), Cd(II) and U(VI) ions onto multi-layered graphene oxide (MLGO). Analysis indicates that the dominant sorption mechanism of Pb to MLGO changes as a function of pH, with increasing inner sphere contribution as pH increases. In contrast, the sorption mechanism of Cd to MLGO remains constant under the studied pH range. This adsorption mechanism is anmore » electrostatic attraction between the hydrated Cd+2 ion and the MLGO surface. The U(VI), present as the uranyl ion, changes only subtly as a function of pH and is bound to the surface via an inner sphere bond. Knowledge of the binding mechanism for each metal is necessary to help in optimizing environmental remediation or prevention in filtration systems.« less

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

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.

Recovering and recycling uranium used for production of molybdenum-99

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

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

A processes for recycling uranium that has been used for the production of molybdenum-99 involves irradiating a solution of uranium suitable for forming fission products including molybdenum-99, conditioning the irradiated solution to one suitable for inducing the formation of crystals of uranyl nitrate hydrates, then forming the crystals and a supernatant and then separating the crystals from the supernatant, thus using the crystals as a source of uranium for recycle. Molybdenum-99 is recovered from the supernatant using an adsorbent such as alumina. Another process involves irradiation of a solid target comprising uranium, forming an acidic solution from the irradiated targetmore » suitable for inducing the formation of crystals of uranyl nitrate hydrates, then forming the crystals and a supernatant and then separating the crystals from the supernatant, thus using the crystals as a source of uranium for recycle. Molybdenum-99 is recovered from the supernatant using an adsorbent such as alumina.« 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.

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

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.

Recent advances in computational actinoid chemistry.

PubMed

Wang, Dongqi; van Gunsteren, Wilfred F; Chai, Zhifang

2012-09-07

We briefly review advances in computational actinoid (An) chemistry during the past ten years in regard to two issues: the geometrical and electronic structures, and reactions. The former addresses the An-O, An-C, and M-An (M is a metal atom including An) bonds in the actinoid molecular systems, including actinoid oxo and oxide species, actinoid-carbenoid, dinuclear and diatomic systems, and the latter the hydration and ligand exchange, the disproportionation, the oxidation, the reduction of uranyl, hydroamination, and the photolysis of uranium azide. Concerning their relevance to the electronic structures and reactions of actinoids and their importance in the development of an advanced nuclear fuel cycle, we also mentioned the work on actinoid carbides and nitrides, which have been proposed to be candidates of the next generation of nuclear fuel, and the oxidation of PuO(x), which is important to understand the speciation of actinoids in the environment, followed by a brief discussion on the urgent need for a heavier involvement of computational actinoid chemistry in developing advanced reprocessing protocols of spent nuclear fuel. The paper is concluded with an outlook.

Theoretical Study of Oxovanadium(IV) Complexation with Formamidoximate: Implications for the Design of Uranyl-Selective Adsorbents

DOE PAGES

Mehio, Nada; Ivanov, Alexander S.; Ladshaw, Austin P.; ...

2015-11-22

Poly(acrylamidoxime) fibers are the current state of the art adsorbent for mining uranium from seawater. However, the competition between uranyl (UO 2 2+) and vanadium ions poses a challenge to mining on the industrial scale. In this work, we employ density functional theory (DFT) and coupled-cluster methods (CCSD(T)) in the restricted formalism to investigate potential binding motifs of the oxovanadium(IV) ion (VO 2+) with the formamidoximate ligand. Consistent with experimental EXAFS data, the hydrated six-coordinate complex is predicted to be preferred over the hydrated five-coordinate complex. Here, our investigation of formamidoximate-VO 2+ complexes universally identified the most stable binding motifmore » formed by chelating a tautomerically rearranged imino hydroxylamine via the imino nitrogen and hydroxylamine oxygen. The alternative binding motifs for amidoxime chelation via a non-rearranged tautomer and 2 coordination are found to be ~11 kcal/mol less stable. Ultimately, the difference in the most stable VO 2+ and UO 2 2+ binding conformation has important implications for the design of more selective UO 2 2+ ligands.« less

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

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

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

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.

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.

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.

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

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

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.

The crystal structure of ianthinite, [U 24+(UO 2) 4O 6(OH) 4(H 2O) 4](H 2O) 5: a possible phase for Pu 4+ incorporation during the oxidation of spent nuclear fuel

NASA Astrophysics Data System (ADS)

Burns, Peter C.; Finch, Robert J.; Hawthorne, Frank C.; Miller, Mark L.; Ewing, Rodney C.

1997-10-01

Ianthinite, [U 24+(UO 2) 4O 6(OH) 4(H 2O) 4](H 2O) 5, is the only known uranyl oxide hydrate mineral that contains U 4+, and it has been proposed that ianthinite may be an important Pu 4+-bearing phase during the oxidative dissolution of spent nuclear fuel. The crystal structure of ianthinite, orthorhombic, a = 0.7178(2), b = 1.1473(2), c = 3.039(1) nm, V = 2.5027 nm 3Z = 4, space group P2 1cn, has been solved by direct methods and refined by least-squares methods to an R index of 9.7% and a wR index of 12.6% using 888 unique observed [| F| ≥ 5 σ | F|] reflections. The structure contains both U 4+. The U 6+ cations are present as roughly linear (U 6+O 2) 2+ uranyl ion (Ur) that are in turn coordinated by five O 2- and OH - located at the equatorial positions of pentagonal bipyramids. The U 4+ cations are coordinated by O 2-, OH - and H 2O in a distorted octahedral arrangement. The Ur φ5and U 4+| 6 (φ: O 2-, OH -, H 2O) polyhedra l sharing edges to for two symmetrically distinct sheets at z ≈ 0.0 and z ≈ 0.25 that are parallel to (001). The sheets have the β-U 3O 8 sheet anion-topology. There are five symmetrically distinct H 2O groips located at z ≈ 0.125 between the sheets of U φn polyhedra, and the sheets of U φn polyhedra are linked together only by hydrogen bonding to the intersheet H 2O groups. The crystal-chemical requirements of U 4+ and Pu 4+ are very similar, suggesting that extensive Pu 4+ ↔ U 4+ substitution may occur within the sheets of U φn polyhedra in trh structure of ianthinine.

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.

Free energies and mechanisms of water exchange around Uranyl from first principles molecular dynamics

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

Atta-Fynn, Raymond; Bylaska, Eric J.; De Jong, Wibe A.

2012-02-01

From density functional theory (DFT) based ab initio (Car-Parrinello) metadynamics, we compute the activation energies and mechanisms of water exchange between the first and second hydration shells of aqueous Uranyl (UO{sub 2}{sup 2+}) using the primary hydration number of U as the reaction coordinate. The free energy and activation barrier of the water dissociation reaction [UO{sub 2}(OH{sub 2}){sub 5}]{sup 2+}(aq) {yields} [UO{sub 2}(OH{sub 2})4]{sup 2+}(aq) + H{sub 2}O are 0.7 kcal and 4.7 kcal/mol respectively. The free energy is in good agreement with previous theoretical (-2.7 to +1.2 kcal/mol) and experimental (0.5 to 2.2 kcal/mol) data. The associative reaction [UO{submore » 2}(OH{sub 2}){sub 5}]{sup 2+}(aq) + H{sub 2}O {yields} [UO{sub 2}(OH{sub 2})6]{sup 2+}(aq) is short-lived with a free energy and activation barrier of +7.9 kcal/mol and +8.9 kca/mol respectively; it is therefore classified as associative-interchange. On the basis of the free energy differences and activation barriers, we predict that the dominant exchange mechanism between [UO{sub 2}(OH{sub 2}){sub 5}]{sup 2+}(aq) and bulk water is dissociative.« less

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

Silver nanoparticle decorated reduced graphene oxide (rGO) nanosheet: a platform for SERS based low-level detection of uranyl ion.

PubMed

Dutta, Soumen; Ray, Chaiti; Sarkar, Sougata; Pradhan, Mukul; Negishi, Yuichi; Pal, Tarasankar

2013-09-11

Herein, a simple wet-chemical pathway has been demonstrated for the synthesis of silver nanoparticle conjugated reduced graphene oxide nanosheets where dimethylformamide (DMF) is judiciously employed as an efficient reducing agent. Altogether, DMF reduces both silver nitrate (AgNO3) and graphene oxide (GO) in the reaction mixture. Additionally, the presence of polyvinylpyrolidone (PVP) assists the nanophasic growth and homogeneous distribution of the plasmonic nanoparticle Ag(0). Reduction of graphene oxide and the presence of aggregated Ag NPs on reduced graphene oxide (rGO) nanosheets are confirmed from various spectroscopic techniques. Finally, the composite material has been exploited as an intriguing platform for surface enhanced Raman scattering (SERS) based selective detection of uranyl (UO2(2+)) ion. The limit of detection has been achieved to be as low as 10 nM. Here the normal Raman spectral (NRS) band of uranyl acetate (UAc) at 838 cm(-1) shifts to 714 and 730 cm(-1) as SERS bands for pH 5.0 and 12.0, respectively. This distinguished Raman shift of the symmetric stretching mode for UO2(2+) ion is indicative of pronounced charge transfer (CT) effect. This CT effect even supports the higher sensitivity of the protocol toward UO2(2+) over other tested oxo-ions. It is anticipated that rGO nanosheets furnish a convenient compartment to favor the interaction between Ag NPs and UO2(2+) ion through proximity induced adsorption even at low concentration.

Summary of the mineralogy of the Colorado Plateau uranium ores

USGS Publications Warehouse

Weeks, Alice D.; Coleman, Robert Griffin; Thompson, Mary E.

1956-01-01

In the Colorado Plateau uranium has been produced chiefly from very shallow mines in carnotite ores (oxidized vanadiferous uranium ores) until recent deeper mining penetrated black unoxidized ores in water-saturated rocks and extensive exploration has discovered many deposits of low to nonvanadiferous ores. The uranium ores include a wide range from highly vanadiferous and from as much as one percent to a trace of copper, and contain a small amount of iron and traces of lead, zinc, molybdenum, cobalt, nickel, silver, manganese, and other metals. Recent investigation indicates that the carnotite ores have been derived by progressive oxidation of primary (unoxidized) black ores that contain low-valent uranium and vanadium oxides and silicates. The uranium minerals, uraninite and coffinite, are associated with coalified wood or other carbonaceous material. The vanadium minerals, chiefly montroseite, roscoelite, and other vanadium silicates, occur in the interstices of the sandstone and in siltstone and clay pellets as well as associated with fossil wood. Calcite, dolomite, barite and minor amounts of sulfides, arsenides, and selenides occur in the unoxidized ore. Partially oxidized vanadiferous ore is blue black, purplish brown, or greenish black in contrast to the black or dark gray unoxidized ore. Vanadium combines with uranium to form rauvite. The excess vanadium is present in corvusite, fernandinite, melanovanadite and many other quadrivalent and quinquevalent vanadium minerals as well as in vanadium silicates. Pyrite and part or all of the calcite are replaced by iron oxides and gypsum. In oxidized vanadiferous uranium ores the uranium is fixed in the relatively insoluble minerals carnotite and tyuyamunite, and the excess vanadium commonly combines with one or more of the following: calcium, sodium, potassium, magnesium, aluminum, iron, copper, manganese, or barium, or rarely it forms the hydrated pentoxide. The relatively stable vanadium silicates are little affected by oxidation. The unoxidized nonvanadiferous ores contain uraninite and coffinite in close association with coalified wood and iron and copper sulfides, and traces of many other sulfides, arsenides and selenides. The oxidized nonvanadiferous ores differ from the vanadiferous ores because, in the absence of vanadium to complex the uranium, a great variety of secondary yellow and greenish-yellow uranyl minerals are formed. The uranyl sulfates and carbonates are more common than the oxides, phosphates, arsenates, and silicates. Because the sulfates and carbonates are much less stable that carnotite, the oxidized nonvanadiferous ores occure only as halos around cores of unoxidized ore and do not form large oxidized deposits close to the surface of the ground as carnotite ores. Oxidation has taken place since the lowering of the water table in the present erosion cycle. Because of local structures and the highly lenticular character of the fluviatile host rocks perched water tables and water-saturated lenses of sandstone are common high above the regional water table. Unoxidized ore has been preserved in these water-saturated rocks and the boundary between oxidized and unoxidized ore is very irregular.

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.

Selective Permeability of Uranyl Peroxide Nanocages to Different Alkali Ions: Influences from Surface Pores and Hydration Shells

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

Gao, Yunyi; Haso, Fadi; Szymanowski, Jennifer E. S.

2015-11-16

The precise guidance to different ions across the biological channels is essential for many biological processes. An artificial nanopore system will facilitate the study of the ion-transport mechanism through nanosized channels and offer new views for designing nanodevices. Herein we reveal that a 2.5 nm-sized, fullerene-shaped molecular cluster Li48+mK12(OH)m[UO2(O2)(OH)]60-(H2O)n (m≈20 and n≈310) (U60) shows selective permeability to different alkali ions. The subnanometer pores on the water–ligand-rich surface of U60 are able to block Rb+ and Cs+ ions from passing through, while allowing Na+ and K+ ions, which possess larger hydrated sizes, to enter the interior space of U60. An interestinglymore » high entropy gain during the binding process between U60 and alkali ions suggests that the hydration shells of Na+/K+ and U60 are damaged during the interaction. The ion selectivity of U60 is greatly influenced by both the morphologies of the surface nanopores and the dynamics of the hydration shells.« less

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)

Plasmachemical synthesis and evaluation of the thermal conductivity of metal-oxide compounds "Molybdenum-uranium dioxide"

NASA Astrophysics Data System (ADS)

Kotelnikova, Alexandra A.; Karengin, Alexander G.; Mendoza, Orlando

2018-03-01

The article represents possibility to apply oxidative and reducing plasma for plasma-chemical synthesis of metal-oxide compounds «Mo‒UO2» from water-salt mixtures «molybdic acid‒uranyl nitrate» and «molybdic acid‒ uranyl acetate». The composition of water-salt mixture was calculated and the conditions ensuring plasma-chemical synthesis of «Mo‒UO2» compounds were determined. Calculations were carried out at atmospheric pressure over a wide range of temperatures (300-4000 K), with the use of various plasma coolants (air, hydrogen). The heat conductivity coefficients of metal-oxide compounds «Mo‒UO2» consisting of continuous component (molybdenum matrix) are calculated. Inclusions from ceramics in the form of uranium dioxide were ordered in the matrix. Particular attention is paid to methods for calculating the coefficients of thermal conductivity of these compounds with the use of different models. Calculated results were compared with the experimental data.

[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

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.

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.

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.

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.

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.

Bacterial methane oxidation in sea-floor gas hydrate: Significance to life in extreme environments

NASA Astrophysics Data System (ADS)

Sassen, Roger; MacDonald, Ian R.; Guinasso, Norman L., Jr.; Joye, Samantha; Requejo, Adolfo G.; Sweet, Stephen T.; Alcalá-Herrera, Javier; Defreitas, Debra A.; Schink, David R.

1998-09-01

Samples of thermogenic hydrocarbon gases, from vents and gas hydrate mounds within a sea-floor chemosynthetic community on the Gulf of Mexico continental slope at about 540 m depth, were collected by research submersible. Our study area is characterized by low water temperature (mean =7 °C), high pressure (about 5400 kPa), and abundant structure II gas hydrate. Bacterial oxidation of hydrate-bound methane (CH4) is indicated by three isotopic properties of gas hydrate samples. Relative to the vent gas from which the gas hydrate formed, (1) methane-bound methane is enriched in 13C by as much as 3.8‰ PDB (Peedee belemnite), (2) hydrate-bound methane is enriched in deuterium (D) by as much as 37‰ SMOW (standard mean ocean water), and (3) hydrate-bound carbon dioxide (CO2) is depleted in 13C by as much as 22.4‰ PDB. Hydrate-associated authigenic carbonate rock is also depleted in 13C. Bacterial oxidation of methane is a driving force in chemosynthetic communities, and in the concomitant precipitation of authigenic carbonate rock that modifies sea-floor geology. Bacterial oxidation of hydrate-bound methane expands the potential boundaries of life in extreme environments.

Anodic Oxidation in Aluminum Electrode by Using Hydrated Amorphous Aluminum Oxide Film as Solid Electrolyte under High Electric Field.

PubMed

Yao, Manwen; Chen, Jianwen; Su, Zhen; Peng, Yong; Zou, Pei; Yao, Xi

2016-05-04

Dense and nonporous amorphous aluminum oxide (AmAO) film was deposited onto platinized silicon substrate by sol-gel and spin coating technology. The evaporated aluminum film was deposited onto the AmAO film as top electrode. The hydrated AmAO film was utilized as a solid electrolyte for anodic oxidation of the aluminum electrode (Al) film under high electric field. The hydrated AmAO film was a high efficiency electrolyte, where a 45 nm thick Al film was anodized completely on a 210 nm thick hydrated AmAO film. The current-voltage (I-V) characteristics and breakdown phenomena of a dry and hydrated 210 nm thick AmAO film with a 150 nm thick Al electrode pad were studied in this work. Breakdown voltage of the dry and hydrated 210 nm thick AmAO film were 85 ± 3 V (405 ± 14 MV m(-1)) and 160 ± 5 V (762 ± 24 MV m(-1)), respectively. The breakdown voltage of the hydrated AmAO film increased about twice, owing to the self-healing behavior (anodic oxidation reaction). As an intuitive phenomenon of the self-healing behavior, priority anodic oxidation phenomena was observed in a 210 nm thick hydrated AmAO film with a 65 nm thick Al electrode pad. The results suggested that self-healing behavior (anodic oxidation reaction) was occurring nearby the defect regions of the films during I-V test. It was an effective electrical self-healing method, which would be able to extend to many other simple and complex oxide dielectrics and various composite structures.

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.

Physiochemical Characterization of Iodine (V) Oxide: Hydration Rates

DTIC Science & Technology

2014-12-15

decomposition .21 2 Distribution A Scheme 1. Iodine (V) Oxide‐Water System Hydration : 3I2O5(s) + H2O(g) → 2HI3O8(s) + 2H2O(g) → 6HIO3(s...dehydration steps and decomposition step for each sample. The corresponding percent compositions of the three hydration forms of the oxide have been...135 Physiochemical Characterization of Iodine (V) Oxide: Hydration Rates Distribution A: Approved for public release; distribution unlimited

The analysis of magnesium oxide hydration in three-phase reaction system

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

Tang, Xiaojia; Guo, Lin; Chen, Chen

In order to investigate the magnesium oxide hydration process in gas–liquid–solid (three-phase) reaction system, magnesium hydroxide was prepared by magnesium oxide hydration in liquid–solid (two-phase) and three-phase reaction systems. A semi-empirical model and the classical shrinking core model were used to fit the experimental data. The fitting result shows that both models describe well the hydration process of three-phase system, while only the semi-empirical model right for the hydration process of two-phase system. The characterization of the hydration product using X-Ray diffraction (XRD) and scanning electron microscope (SEM) was performed. The XRD and SEM show hydration process in the two-phasemore » system follows common dissolution/precipitation mechanism. While in the three-phase system, the hydration process undergo MgO dissolution, Mg(OH){sub 2} precipitation, Mg(OH){sub 2} peeling off from MgO particle and leaving behind fresh MgO surface. - Graphical abstract: There was existence of a peeling-off process in the gas–liquid–solid (three-phase) MgO hydration system. - Highlights: • Magnesium oxide hydration in gas–liquid–solid system was investigated. • The experimental data in three-phase system could be fitted well by two models. • The morphology analysis suggested that there was existence of a peel-off process.« less

Adsorption of gluconate and uranyl on C-S-H phases: Combination of wet chemistry experiments and molecular dynamics simulations for the binary systems

NASA Astrophysics Data System (ADS)

Androniuk, Iuliia; Landesman, Catherine; Henocq, Pierre; Kalinichev, Andrey G.

2017-06-01

As a first step in developing better molecular scale understanding of the effects of organic additives on the adsorption and mobility of radionuclides in cement under conditions of geological nuclear waste repositories, two complementary approaches, wet chemistry experiments and molecular dynamics (MD) computer simulations, were applied to study the sorption behaviour of two simple model systems: gluconate and uranyl on calcium silicate hydrate phases (C-S-H) - the principal mineral component of hardened cement paste (HCP). Experimental data on sorption and desorption kinetics and isotherms of adsorption for gluconate/C-S-H and U(VI)/C-S-H binary systems were collected and quantitatively analysed for C-S-H samples synthesised with various Ca/Si ratios (0.83, 1.0, 1.4) corresponding to various stages of HCP aging and degradation. Gluconate labelled with 14C isotope was used in order to improve the sensitivity of analytical detection technique (LSC) at particularly low concentrations (10-8-10-5 mol/L). There is a noticeable effect of Ca/Si ratio on the gluconate sorption on C-S-H, with stronger sorption at higher Ca/Si ratios. Sorption of organic anions on C-S-H is mediated by the presence of Ca2+ at the interface and strongly depends on the surface charge and Ca2+ concentration. In parallel, classical MD simulations of the same model systems were performed in order to identify specific surface sorption sites most actively involved in the sorption of gluconate and uranyl on C-S-H and to clarify molecular mechanisms of adsorption.

Actinide metal processing

DOEpatents

Sauer, Nancy N.; Watkin, John G.

1992-01-01

A process of converting an actinide metal such as thorium, uranium, or plnium to an actinide oxide material by admixing the actinide metal in an aqueous medium with a hypochlorite as an oxidizing agent for sufficient time to form the actinide oxide material and recovering the actinide oxide material is provided together with a low temperature process of preparing an actinide oxide nitrate such as uranyl nitrte. Additionally, a composition of matter comprising the reaction product of uranium metal and sodium hypochlorite is provided, the reaction product being an essentially insoluble uranium oxide material suitable for disposal or long term storage.

Actinide metal processing

DOEpatents

Sauer, N.N.; Watkin, J.G.

1992-03-24

A process for converting an actinide metal such as thorium, uranium, or plutonium to an actinide oxide material by admixing the actinide metal in an aqueous medium with a hypochlorite as an oxidizing agent for sufficient time to form the actinide oxide material and recovering the actinide oxide material is described together with a low temperature process for preparing an actinide oxide nitrate such as uranyl nitrate. Additionally, a composition of matter comprising the reaction product of uranium metal and sodium hypochlorite is provided, the reaction product being an essentially insoluble uranium oxide material suitable for disposal or long term storage.

Inhibited phase behavior of gas hydrates in graphene oxide: influences of surface and geometric constraints.

PubMed

Kim, Daeok; Kim, Dae Woo; Lim, Hyung-Kyu; Jeon, Jiwon; Kim, Hyungjun; Jung, Hee-Tae; Lee, Huen

2014-11-07

Porous materials have provided us unprecedented opportunities to develop emerging technologies such as molecular storage systems and separation mechanisms. Pores have also been used as supports to contain gas hydrates for the application in gas treatments. Necessarily, an exact understanding of the properties of gas hydrates in confining pores is important. Here, we investigated the formation of CO2, CH4 and N2 hydrates in non-interlamellar voids in graphene oxide (GO), and their thermodynamic behaviors. For that, low temperature XRD and P-T traces were conducted to analyze the water structure and confirm hydrate formation, respectively, in GO after its exposure to gaseous molecules. Confinement and strong interaction of water with the hydrophilic surface of graphene oxide reduce water activity, which leads to the inhibited phase behavior of gas hydrates.

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.

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.

Purification of uranium alloys by differential solubility of oxides and production of purified fuel precursors

DOEpatents

McLean, II, William; Miller, Philip E.

1997-01-01

A method for purifying metallic alloys of uranium for use as nuclear reactor fuels in which the metal alloy is first converted to an oxide and then dissolved in nitric acid. Initial removal of metal oxide impurities not soluble in nitric acid is accomplished by filtration or other physical means. Further purification can be accomplished by carbonate leaching of uranyl ions from the partially purified solution or using traditional methods such as solvent extraction.

Purification of uranium alloys by differential solubility of oxides and production of purified fuel precursors

DOEpatents

McLean, W. II; Miller, P.E.

1997-12-16

A method is described for purifying metallic alloys of uranium for use as nuclear reactor fuels in which the metal alloy is first converted to an oxide and then dissolved in nitric acid. Initial removal of metal oxide impurities not soluble in nitric acid is accomplished by filtration or other physical means. Further purification can be accomplished by carbonate leaching of uranyl ions from the partially purified solution or using traditional methods such as solvent extraction. 3 figs.

Unprecedented reduction of the uranyl ion [UO2]2+ into a polyoxo uranium(IV) cluster: synthesis and crystal structure of the first f-element oxide with a M6(micro3-O)8 core.

PubMed

Berthet, Jean-Claude; Thuéry, Pierre; Ephritikhine, Michel

2005-07-21

The smooth comproportionation reaction of the U(VI) and U(III) complexes UO2(OTf)2 and U(OTf)3, afforded the hexanuclear U(IV) oxide cluster [U6(micro3-O)8(micro2-OTf)8(py)8], a rare example of a metal oxide with a M6(micro3-O)8 core.

From Layered Structures to Cubic Frameworks. Expanding the Structural Diversity of Uranyl Carboxyphosphonates via the Incorporation of Cobalt

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

Alsobrook, Andrea N.; Hauser, Brad G.; Hupp, Joseph T.

2011-02-08

Five heterobimetallic U(VI)/Co(II) carboxyphosphonates have been synthesized under mild hydrothermal conditions by reacting UO 3, Co(CH 3CO 2) 2·4H 2O, and triethyl phosphonoacetate. These compounds, Co(H 2O) 4[(UO 2) 2(PO 3CH 2CO 2) 2(H 2O) 2] (CoUPAA-1), [Co(H 2O) 6][UO 2(PO 3CH 2CO 2)] 2·8H 2O (CoUPAA-2), Co(H 2O) 4[UO 2(PO 3CH 2CO 2)] 2·4H 2O (CoUPAA-3), Co(H 2O) 4[(UO 2) 62CH 2CO 2) 2O 2(OH) 3(H 2O) 3] 2·3H 2O (CoUPAA-4), and Co 2(UO 2) 6(PO 3CH 2CO 2) 3O 3(OH)(H 2O) 2·16H 2O (CoUPAA-5), range from two- to three-dimensional structures. CoUPAA-1 to CoUPAA-3 all possess uranyl carboxyphosphonate layersmore » that are separated by the Co(II) cation with varying degrees of hydration. CoUPAA-4 contains both UO 7 pentagonal bipyramids and UO 8 hexagonal bipyramids within the uranyl carboxyphosphonate plane. Unlike the first four low-symmetry compounds, CoUPAA-5 is a cubic, three-dimensional network with large cavities approximately 16 Å in diameter that are filled with cocrystallized water molecules. Differential gas absorption measurements performed on CoUPAA-5 displayed a surface area uptake for CO 2 of 40 m 2 g -1 at 273 K, and no uptake for N 2 at 77 K.« less

Hydration behaviors of calcium silicate-based biomaterials.

PubMed

Lee, Yuan-Ling; Wang, Wen-Hsi; Lin, Feng-Huie; Lin, Chun-Pin

2017-06-01

Calcium silicate (CS)-based biomaterials, such as mineral trioxide aggregate (MTA), have become the most popular and convincing material used in restorative endodontic treatments. However, the commercially available CS-based biomaterials all contain different minor additives, which may affect their hydration behaviors and material properties. The purpose of this study was to evaluate the hydration behavior of CS-based biomaterials with/without minor additives. A novel CS-based biomaterial with a simplified composition, without mineral oxides as minor additives, was produced. The characteristics of this biomaterial during hydration were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectrometry. The hydration behaviors of commercially available gray and white MTAs with mineral oxide as minor additives were also evaluated for reference. For all three test materials, the XRD analysis revealed similar diffraction patterns after hydration, but MTAs presented a significant decrease in the intensities of Bi 2 O 3 -related peaks. SEM results demonstrated similar porous microstructures with some hexagonal and facetted crystals on the outer surfaces. In addition, compared to CS with a simplified composition, the FTIR plot indicated that hydrated MTAs with mineral oxides were better for the polymerization of calcium silicate hydrate (CSH), presenting Si-O band shifting to higher wave numbers, and contained more water crystals within CSH, presenting sharper bands for O-H bending. Mineral oxides might not result in significant changes in the crystal phases or microstructures during the hydration of CS-based biomaterials, but these compounds affected the hydration behavior at the molecular level. Copyright © 2016. Published by Elsevier B.V.

Incorporation of oxidized uranium into Fe (hydr)oxides during Fe(II) catalyzed remineralization

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

Nico, Peter S.; Stewart, Brandy D.; Fendorf, Scott

2009-07-01

The form of solid phase U after Fe(II) induced anaerobic remineralization of ferrihydrite in the presence of aqueous and absorbed U(VI) was investigated under both abiotic batch and biotic flow conditions. Experiments were conducted with synthetic ground waters containing 0.168 mM U(VI), 3.8 mM carbonate, and 3.0 mM Ca{sup 2+}. In spite of the high solubility of U(VI) under these conditions, appreciable removal of U(VI) from solution was observed in both the abiotic and biotic systems. The majority of the removed U was determined to be substituted as oxidized U (U(VI) or U(V)) into the octahedral position of the goethitemore » and magnetite formed during ferrihydrite remineralization. It is estimated that between 3% and 6% of octahedral Fe(III) centers in the new Fe minerals were occupied by U(VI). This site specific substitution is distinct from the non-specific U co-precipitation processes in which uranyl compounds, e.g. uranyl hydroxide or carbonate, are entrapped with newly formed Fe oxides. The prevalence of site specific U incorporation under both abiotic and biotic conditions and the fact that the produced solids were shown to be resistant to both extraction (30 mM KHCO{sub 3}) and oxidation (air for 5 days) suggest the potential importance of sequestration in Fe oxides as a stable and immobile form of U in the environment.« less

Proteomic analysis reveals contrasting stress response to uranium in two nitrogen-fixing Anabaena strains, differentially tolerant to uranium.

PubMed

Panda, Bandita; Basu, Bhakti; Acharya, Celin; Rajaram, Hema; Apte, Shree Kumar

2017-01-01

Two strains of the nitrogen-fixing cyanobacterium Anabaena, native to Indian paddy fields, displayed differential sensitivity to exposure to uranyl carbonate at neutral pH. Anabaena sp. strain PCC 7120 and Anabaena sp. strain L-31 displayed 50% reduction in survival (LD 50 dose), following 3h exposure to 75μM and 200μM uranyl carbonate, respectively. Uranium responsive proteome alterations were visualized by 2D gel electrophoresis, followed by protein identification by MALDI-ToF mass spectrometry. The two strains displayed significant differences in levels of proteins associated with photosynthesis, carbon metabolism, and oxidative stress alleviation, commensurate with their uranium tolerance. Higher uranium tolerance of Anabaena sp. strain L-31 could be attributed to sustained photosynthesis and carbon metabolism and superior oxidative stress defense, as compared to the uranium sensitive Anabaena sp. strain PCC 7120. Uranium responsive proteome modulations in two nitrogen-fixing strains of Anabaena, native to Indian paddy fields, revealed that rapid adaptation to better oxidative stress management, and maintenance of metabolic and energy homeostasis underlies superior uranium tolerance of Anabaena sp. strain L-31 compared to Anabaena sp. strain PCC 7120. Copyright © 2016 Elsevier B.V. All rights reserved.

Hydration characteristics of zirconium oxide replaced Portland cement for use as a root-end filling material.

PubMed

Camilleri, J; Cutajar, A; Mallia, B

2011-08-01

Zirconium oxide can be added to dental materials rendering them sufficiently radiopaque. It can thus be used to replace the bismuth oxide in mineral trioxide aggregate (MTA). Replacement of Portland cement with 30% zirconium oxide mixed at a water/cement ratio of 0.3 resulted in a material with adequate physical properties. This study aimed at investigating the microstructure, pH and leaching in physiological solution of Portland cement replaced zirconium oxide at either water-powder or water-cement ratios of 0.3 for use as a root-end filling material. The hydration characteristics of the materials which exhibited optimal behavior were evaluated. Portland cement replaced by zirconium oxide in varying amounts ranging from 0 to 50% in increments of 10 was prepared and divided into two sets. One set was prepared at a constant water/cement ratio while the other set at a constant water/powder ratio of 0.3. Portland cement and MTA were used as controls. The materials were analyzed under the scanning electron microscope (SEM) and the hydration products were determined. X-ray energy dispersive analysis (EDX) was used to analyze the elemental composition of the hydration products. The pH and the amount of leachate in Hank's balanced salt solution (HBSS) were evaluated. A material that had optimal properties that satisfied set criteria and could replace MTA was selected. The microstructure of the prototype material and Portland cement used as a control was assessed after 30 days using SEM and atomic ratio diagrams of Al/Ca versus Si/Ca and S/Ca versus Al/Ca were plotted. The hydration products of Portland cement replaced with 30% zirconium oxide mixed at water/cement ratio of 0.3 were calcium silicate hydrate, calcium hydroxide and minimal amounts of ettringite and monosulphate. The calcium hydroxide leached in HBSS solution resulted in an increase in the pH value. The zirconium oxide acted as inert filler and exhibited no reaction with the hydration by-products of Portland cement. A prototype dental material composed of Portland cement replaced with 30% zirconium oxide as radiopacifier leached calcium ions on hydration which reacted with phosphates present in simulated tissue fluids. This resulted in bioactive cement that could prospectively be used as a root-end filling material. The zirconium oxide acted as inert filler and did not participate in the hydration reaction of the Portland cement. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Theoretical study of the coordination behavior of formate and formamidoximate with dioxovanadium( v ) cation: implications for selectivity towards uranyl

DOE PAGES

Mehio, Nada; Johnson, J. Casey; Dai, Sheng; ...

2015-10-28

Poly(acrylamidoxime)-based fibers bearing random mixtures of carboxylate and amidoxime groups are the most widely utilized materials for extracting uranium from seawater. However, the competition between uranyl (UO 2 2+) and vanadium ions poses a significant challenge to the industrial mining of uranium from seawater using the current generation of adsorbents. To design more selective adsorbents, a detailed understanding of how major competing ions interact with carboxylate and amidoxime ligands is required. In this work, we employ density functional theory (DFT) and wave-function methods to investigate potential binding motifs of the dioxovanadium ion, VO 2 +, with water, formate, and formamidoximatemore » ligands. Employing higher level of theory calculations (CCSD(T)) resolve the existing controversy between the experimental results and previous DFT calculations for the structure of the hydrated VO 2 + ion. Consistent with the EXAFS data, CCSD(T) calculations predict higher stability of the distorted octahedral geometry of VO 2 +(H 2O) 4 compared to the five-coordinate complex with a single water molecule in the second hydration shell, while all seven tested DFT methods yield the reverse stability of the two conformations. Analysis of the relative stabilities of formate-VO 2 + complexes indicates that both monodentate and bidentate forms may coexist in thermodynamic equilibrium in solution, with the equilibrium balance leaning more towards the formation of monodentate species. Investigations of VO 2 + coordination with the formamidoximate anion has revealed the existence of seven possible binding motifs, four of which are within ~ 4.0 kcal/mol of each other. Calculations establish that the most stable binding motif entails the coordination of oxime oxygen and amide nitrogen atoms via a tautomeric rearrangement of amidoxime to imino hydroxylamine. Lastly, the difference in the most stable VO 2 + and UO 2 2+ binding conformation has important implications for the design of more selective UO 2 2+ ligands.« less

Assembling tungsten oxide hydrate nanocrystal colloids formed by laser ablation in liquid into fast-response electrochromic films.

PubMed

Wang, Shalong; Dou, Kang; Zou, Yousheng; Dong, Yuhang; Li, Jubin; Ju, Dan; Zeng, Haibo

2017-03-01

High-performance electrochromic films based on tungsten oxide hydrate ([WO 2 (O 2 )H 2 O]·1.66H 2 O) colloidal nanocrystals with fast switching speed were fabricated by laser ablation in a mixture of water and hydrogen peroxide followed by electrophoretic methods. Through electrophoretic deposition, the nanoparticles in the colloids synthesized by laser ablation aggregated onto the FTO coated glass substrate forming a lager cell with a uniform size of around 200nm, which subsequently self-assembled into a porous tungsten oxide hydrate film. By optimizing the electrophoretic time (800s) and voltage (-0.5V), the mesh-like porous tungsten oxide hydrate film achieved a wide optical modulation of 32% at 632nm, fast coloration and bleaching response speed of 7.8 s and 1.7s respectively due to the synergetic effect of the unique atomic structure of [WO 2 (O 2 )H 2 O]·1.66H 2 O and porous structure with large surface area that facilitates the ion insertion/extraction. Thus the tungsten oxide hydrate can be a promising electrochromic material for practical applications. Copyright © 2016 Elsevier Inc. All rights reserved.

Studies on the protective effect of dietary fish oil on uranyl-nitrate-induced nephrotoxicity and oxidative damage in rat kidney.

PubMed

Priyamvada, Shubha; Khan, Sara A; Khan, Md Wasim; Khan, Sheeba; Farooq, Neelam; Khan, Farah; Yusufi, A N K

2010-01-01

Human and animal exposure demonstrates that uranium is nephrotoxic. However, attempts to reduce it were not found suitable for clinical use. Dietary fish oil (FO) enriched in omega-3 fatty acids reduces the severity of cardiovascular and renal diseases. Present study investigates the protective effect of FO on uranyl nitrate (UN)-induced renal damage. Rats prefed with experimental diets for 15 days, given single nephrotoxic dose of UN (0.5mg/kg body weight) intraperitoneally. After 5d of UN treatment, serum/urine parameters, enzymes of carbohydrate metabolism, brush border membrane (BBM), oxidative stress and phosphate transport were analyzed in rat kidney. UN nephrotoxicity was characterized by increased serum creatinine and blood urea nitrogen. UN increased the activity of lactate dehydrogenase and NADP-malic enzyme whereas decreased malate, isocitrate and glucose-6-phophate dehydrogenases; glucose-6-phophatase, fructose-1, 6-bisphosphatase and BBM enzyme activities. UN caused oxidant/antioxidant imbalances as reflected by increased lipid peroxidation, activities of superoxide dismutase, glutathione peroxidase and decreased catalase activity. Feeding FO alone increased activities of enzymes of glucose metabolism, BBM, oxidative stress and Pi transport. UN-elicited alterations were prevented by FO feeding. However, corn oil had no such effects and was not similarly effective. In conclusion, FO appears to protect against UN-induced nephrotoxicity by improving energy metabolism and antioxidant defense mechanism. Copyright 2009 Elsevier Ltd. All rights reserved.

NMR relaxometry study of cement hydration in the presence of different oxidic fine fraction materials.

PubMed

Nestle, Nikolaus

2004-01-01

NMR relaxometry has been applied to study hydrating cements for about 25 years now. The most important advantage over other experimental approaches is the possibility to conduct non-destructive measurements with a time resolution of minutes. NMR relaxometry data thus can help to identify details in the time course of cement hydration that possibly would be overlooked in other experiments with lower temporal resolution. Time-resolved information on cement hydration kinetics can provide interesting insights into the impact of oxidic additive materials on cement hydration. For PbO, a very strong delay was observed which then was systematically studied. An explanation for this delay is suggested.

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.

Roll-to-Roll Processing of Inverted Polymer Solar Cells using Hydrated Vanadium(V)Oxide as a PEDOT:PSS Replacement

PubMed Central

Espinosa, Nieves; Dam, Henrik Friis; Tanenbaum, David M.; Andreasen, Jens W.; Jørgensen, Mikkel; Krebs, Frederik C.

2011-01-01

The use of hydrated vanadium(V)oxide as a replacement of the commonly employed hole transporting material PEDOT:PSS was explored in this work. Polymer solar cells were prepared by spin coating on glass. Polymer solar cells and modules comprising 16 serially connected cells were prepared using full roll-to-roll (R2R) processing of all layers. The devices were prepared on flexible polyethyleneterphthalate (PET) and had the structure PET/ITO/ZnO/P3HT:PCBM/V2O5·(H2O)n/Ag. The ITO and silver electrodes were processed and patterned by use of screen printing. The zinc oxide, P3HT:PCBM and vanadium(V)oxide layers were processed by slot-die coating. The hydrated vanadium(V)oxide layer was slot-die coated using an isopropanol solution of vanadyl-triisopropoxide (VTIP). Coating experiments were carried out to establish the critical thickness of the hydrated vanadium(V)oxide layer by varying the concentration of the VTIP precursor over two orders of magnitude. Hydrated vanadium(V)oxide layers were characterized by profilometry, scanning electron microscopy, energy dispersive X-ray spectroscopy, and grazing incidence wide angle X-ray scattering. The power conversion efficiency (PCE) for completed modules was up to 0.18%, in contrast to single cells where efficiencies of 0.4% were achieved. Stability tests under indoor and outdoor conditions were accomplished over three weeks on a solar tracker. PMID:28879984

Roll-to-Roll Processing of Inverted Polymer Solar Cells using Hydrated Vanadium(V)Oxide as a PEDOT:PSS Replacement.

PubMed

Espinosa, Nieves; Dam, Henrik Friis; Tanenbaum, David M; Andreasen, Jens W; Jørgensen, Mikkel; Krebs, Frederik C

2011-01-11

The use of hydrated vanadium(V)oxide as a replacement of the commonly employed hole transporting material PEDOT:PSS was explored in this work. Polymer solar cells were prepared by spin coating on glass. Polymer solar cells and modules comprising 16 serially connected cells were prepared using full roll-to-roll (R2R) processing of all layers. The devices were prepared on flexible polyethyleneterphthalate (PET) and had the structure PET/ITO/ZnO/P3HT:PCBM/V₂O₅·(H₂O) n /Ag. The ITO and silver electrodes were processed and patterned by use of screen printing. The zinc oxide, P3HT:PCBM and vanadium(V)oxide layers were processed by slot-die coating. The hydrated vanadium(V)oxide layer was slot-die coated using an isopropanol solution of vanadyl-triisopropoxide (VTIP). Coating experiments were carried out to establish the critical thickness of the hydrated vanadium(V)oxide layer by varying the concentration of the VTIP precursor over two orders of magnitude. Hydrated vanadium(V)oxide layers were characterized by profilometry, scanning electron microscopy, energy dispersive X-ray spectroscopy, and grazing incidence wide angle X-ray scattering. The power conversion efficiency (PCE) for completed modules was up to 0.18%, in contrast to single cells where efficiencies of 0.4% were achieved. Stability tests under indoor and outdoor conditions were accomplished over three weeks on a solar tracker.

Competing retention pathways of uranium upon reaction with Fe(II)

NASA Astrophysics Data System (ADS)

Massey, Michael S.; Lezama-Pacheco, Juan S.; Jones, Morris E.; Ilton, Eugene S.; Cerrato, José M.; Bargar, John R.; Fendorf, Scott

2014-10-01

Biogeochemical retention processes, including adsorption, reductive precipitation, and incorporation into host minerals, are important in contaminant transport, remediation, and geologic deposition of uranium. Recent work has shown that U can become incorporated into iron (hydr)oxide minerals, with a key pathway arising from Fe(II)-induced transformation of ferrihydrite, (Fe(OH)3·nH2O) to goethite (α-FeO(OH)); this is a possible U retention mechanism in soils and sediments. Several key questions, however, remain unanswered regarding U incorporation into iron (hydr)oxides and this pathway's contribution to U retention, including: (i) the competitiveness of U incorporation versus reduction to U(IV) and subsequent precipitation of UO2; (ii) the oxidation state of incorporated U; (iii) the effects of uranyl aqueous speciation on U incorporation; and, (iv) the mechanism of U incorporation. Here we use a series of batch reactions conducted at pH ∼7, [U(VI)] from 1 to 170 μM, [Fe(II)] from 0 to 3 mM, and [Ca] at 0 or 4 mM coupled with spectroscopic examination of reaction products of Fe(II)-induced ferrihydrite transformation to address these outstanding questions. Uranium retention pathways were identified and quantified using extended X-ray absorption fine structure (EXAFS) spectroscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. Analysis of EXAFS spectra showed that 14-89% of total U was incorporated into goethite, upon reaction with Fe(II) and ferrihydrite. Uranium incorporation was a particularly dominant retention pathway at U concentrations ⩽50 μM when either uranyl-carbonato or calcium-uranyl-carbonato complexes were dominant, accounting for 64-89% of total U. With increasing U(VI) and Fe(II) concentrations, U(VI) reduction to U(IV) became more prevalent, but U incorporation remained a functioning retention pathway. These findings highlight the potential importance of U(V) incorporation within iron oxides as a retention process of U across a wide range of biogeochemical environments and the sensitivity of uranium retention processes to operative (bio)geochemical conditions.

Competing retention pathways of uranium upon reaction with Fe(II)

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

Massey, Michael S.; Lezama Pacheco, Juan S.; Jones, Morris

Biogeochemical retention processes, including adsorption, reductive precipitation, and incorporation into host minerals, are important in contaminant transport, remediation, and geologic deposition of uranium. Recent work has shown that U can become incorporated into iron (hydr)oxide minerals, with a key pathway arising from Fe(II)-induced transformation of ferrihydrite, (Fe(OH)3•nH2O) to goethite (α-FeO(OH)); this is a possible U retention mechanism in soils and sediments. Several key questions, however, remain unanswered regarding U incorporation into iron (hydr)oxides and this pathway’s contribution to U retention, including: (i) the competitiveness of U incorporation versus reduction to U(IV) and subsequent precipitation of UO2; (ii) the oxidation statemore » of incorporated U; (iii) the effects of uranyl aqueous speciation on U incorporation; and, (iv) the mechanism of U incorporation. Here we use a series of batch reactions conducted at pH ~7, [U(VI)] from 1 to 170 μM, [Fe(II)] from 0 to 3 mM, and [Ca] at 0 or 4 mM) coupled with spectroscopic examination of reaction products of Fe(II)-induced ferrihydrite transformation to address these outstanding questions. Uranium retention pathways were identified and quantified using extended x-ray absorption fine structure (EXAFS) spectroscopy, x-ray powder diffraction, x-ray photoelectron spectroscopy, and transmission electron microscopy. Analysis of EXAFS spectra showed that 14 to 89% of total U was incorporated into goethite, upon reaction with Fe(II) and ferrihydrite. Uranium incorporation was a particularly dominant retention pathway at U concentrations ≤ 50 μM when either uranyl-carbonato or calcium-uranyl-carbonato complexes were dominant, accounting for 64 to 89% of total U. With increasing U(VI) and Fe(II) concentrations, U(VI) reduction to U(IV) became more prevalent, but U incorporation remained a functioning retention pathway. These findings highlight the potential importance of U(V) incorporation within iron oxides as a retention process of U across a wide range of biogeochemical environments and the sensitivity of uranium retention processes to operative (bio)geochemical conditions.« 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.

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

Rust in the Apollo 16 rocks. [hydration and oxidation processes in lunar environment

NASA Technical Reports Server (NTRS)

Taylor, L. A.; Mao, H. K.; Bell, P. M.

1973-01-01

Apollo 16 samples of all four rock types and from all stations contain evidence for hydration and oxidation - i.e., the presence of hydrated iron oxide, probably goethite. Rock 66095 contains native FeNi grains with a characteristic intergrowth of schreibersite and, to lesser extents, of cohenite. Troilite also contains sphalerite. The goethite contains 1.5-4.6 wt.% chlorine and occurs mainly on the edges of FeNi metal, causing a rust color in the cracks and space around the native metal grains, which also contain abundant chlorine. This observation suggests the presence of lawrencite (FeCl2), a phase that deliquesces and oxidizes very rapidly upon exposure to water or to a moist atmosphere.

Using Demonstrations Involving Combustion and Acid-Base Chemistry to Show Hydration of Carbon Dioxide, Sulfur Dioxide, and Magnesium Oxide and Their Relevance for Environmental Climate Science

ERIC Educational Resources Information Center

Shaw, C. Frank, III; Webb, James W.; Rothenberger, Otis

2016-01-01

The nature of acidic and basic (alkaline) oxides can be easily illustrated via a series of three straightforward classroom demonstrations for high school and general chemistry courses. Properties of carbon dioxide, sulfur dioxide, and magnesium oxide are revealed inexpensively and safely. Additionally, the very different kinetics of hydration of…

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.

A laboratory study of anaerobic oxidation of methane in the presence of methane hydrate

NASA Astrophysics Data System (ADS)

Solem, R.; Bartlett, D.; Kastner, M.; Valentine, D.

2003-12-01

In order to mimic and study the process of anaerobic methane oxidation in methane hydrate regions we developed four high-pressure anaerobic bioreactors, designed to incubate environmental sediment samples, and enrich for populations of microbes associated with anaerobic methane oxidation (AMO). We obtained sediment inocula from a bacterial mat at the southern Hydrate Ridge, Cascadia, having cell counts approaching 1010 cells/cc. Ultimately, our goal is to produce an enriched culture of these microbes for characterization of the biochemical processes and chemical fluxes involved, as well as the unique adaptations required for, AMO. Molecular phylogenetic information along with results from fluorescent in situ hybridization indicate that consortia of Archaea and Bacteria are present which are related to those previously described for marine sediment AMO environments. Using a medium of enriched seawater and sediment in a 3:1 ratio, the system was incubated at 4° C under 43 atm of methane pressure; the temperature and pressure were kept constant. We have followed the reactions for seven months, particularly the vigorous consumption rates of dissolved sulfate and alkalinity production, as well as increases in HS-, and decreases in Ca concentrations. We also monitored the dissolved inorganic C (DIC) δ 13C values. The data were reproduced, and indicated that the process is extremely sensitive to changes in methane pressure. The rates of decrease in sulfate and increase in alkalinity concentrations were complimentary and showed considerable linearity with time. When the pressure in the reactor was decreased below the methane hydrate stability field, following the methane hydrate dissociation, sulfate reduction abruptly decreased. When the pressure was restored all the reactions returned to their previous rates. Much of the methane oxidation activity in the reactor is believed to occur in association with the methane hydrate. Upon the completion of one of the experiments, the chamber methane hydrate, liquid phase, and sediment were separated. FISH analyses of the dissociated hydrate fluid indicate a significant presence of Archaea in or on the hydrate. The cell densities in the bioreactor medium liquid phase were 7.2 x 107 cells/cc, and with the methane hydrate, 2.8 x 108 cells/cc.

Multi-step oxidations catalyzed by cytochrome P450 enzymes: Processive vs. distributive kinetics and the issue of carbonyl oxidation in chemical mechanisms

PubMed Central

Guengerich, F. Peter; Sohl, Christal D.; Chowdhury, Goutam

2010-01-01

Catalysis of sequential oxidation reactions is not unusual in cytochrome P450 (P450) reactions, not only in steroid metabolism but also with many xenobiotics. One issue is how processive/distributive these reactions are, i.e. how much do the “intermediate” products dissociate. Our work with human P450s 2E1, 2A6, and 19A1 on this subject has revealed a mixture of systems, surprisingly with a more distributive mechanism with an endogenous substrate (P450 19A1) than for some xenobiotics (P450s 2E1, 2A6). One aspect of this research involves carbonyl intermediates, and the choice of catalytic mechanism is linked to the hydration state of the aldehyde. The non-enzymatic rates of hydration and dehydration of carbonyls are not rapid and whether P450s catalyze the reversible hydration is unknown. If carbonyl hydration and dehydration are slow, the mechanism may be set by the carbonyl hydration status. PMID:20804723

Low-temperature interaction of U(IV) and XeO{sub 3} in frozen aqueous H{sub 2}SO{sub 4} solutions accompanied by chemiluminescence

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

Lotnik, S.V.; Khamidullina, L.A.; Kazakov, V.P.

Low-temperature (T{ge}180K) oxidation of U(IV) by xenon trioxide accompanied by chemiluminescence is studied in a frozen 0.2 M H{sub 2}SO{sub 4} solution. It is shown that the peak of luminescence at 195-200 K is related to chemiluminescence of the excited uranyl ion (UO{sup 2+}{sub 2}) formed in the oxidation of U(V), an intermediate product of the interaction of U(IV) and XeO{sub 3}.

Morin hydrate mitigates rapid eye movement sleep deprivation-induced neurobehavioural impairments and loss of viable neurons in the hippocampus of mice.

PubMed

Olonode, Elizabeth T; Aderibigbe, Adegbuyi O; Adeoluwa, Olusegun A; Eduviere, Anthony T; Ben-Azu, Benneth

2017-12-25

Rapid eye movement sleep deprivation distorts the body's homeostasis and results in oxidative breakdown which may be responsible for a variety of neurological disorders. Some naturally occurring compounds of plant origin with antioxidant and neuroprotective properties are known to attenuate the detrimental effects of REM sleep deprivation. Morin hydrate, a flavonoid from Mulberry has demonstrated antioxidant and neuroprotective activities but its effect in sleep disturbed mice is unknown. The study was designed to explore the neuroprotective effect of Morin hydrate on 48 h. REM sleep deprivation-induced behavioural impairments and neuronal damage in mice. Mice were allotted into six treatment groups (n = 6): groups 1 and 2 received vehicle (10 ml/kg normal saline), groups 3-5 received Morin hydrate (5, 10, 20 mg/kg i.p) while group 6 received ginseng (25 mg/kg) which served as the reference drug. Treatment was performed daily for 5 days and animals were sleep-deprived on the last 48 h. Various behavioural tests (Elevated plus maze, Y-maze, locomotor activity) followed by oxidative parameters (malondialdehyde, nitric oxide, reduced glutathione) and histolopathological changes in the Cornu ammonis 1 (CA1) region of the hippocampus were assessed. Data were analysed using ANOVA at α 0.05 . Morin hydrate (5, 10, 20 mg/kg) significantly enhanced memory performance, improves anxiolytic-like behaviour, reverses hyperlocomotion, restored depleted reduced glutathione, attenuated raised malondialdehyde and nitric oxide levels as compared to control animals and protects against loss of hippocampal neurons. Results of this present study suggest that Morin hydrate possess neuroprotective effects against sleep deprivation-induced behavioural impairments, oxidative stress and neuronal damage. Copyright © 2017 Elsevier B.V. All rights reserved.

The effect of protein oxidation on hydration and water-binding in pork packaged in an oxygen-enriched atmosphere.

PubMed

Delles, Rebecca M; Xiong, Youling L

2014-06-01

This study investigated the in situ oxidative process of myofibrillar proteins in boneless pork loin chops (Longissimus lumborum) packaged in an oxygen-enriched atmosphere (HiOx: 80% O2/20% CO2), an air-permeable polyvinylchloride (PVC) overwrap, or a partial vacuum (VP) throughout display at 2°C for up to 14, 7, and 21days, respectively. Samples stored in HiOx were susceptible to lipid (TBARS) and protein (carbonyls, sulfhydryls, and aggregation) oxidation, while samples in PVC and VP showed lesser oxidative changes. Water-holding capacity of raw muscle decreased (P<0.05) when stored in HiOx but not in PVC and VP. Upon salt and phosphate brine marination, HiOx and PVC muscle samples had improved hydration capacity during display compared with non-stored control, but display generally decreased hydration of VP samples. The result was in agreement with myofibril structural changes. Despite the enhanced hydration, HiOx muscle was least capable of withholding moisture upon cooking. Copyright © 2014 Elsevier Ltd. All rights reserved.

Photoelectrochemical generation of hydrogen and electricity from hydrazine hydrate using BiVO4 electrodes.

PubMed

Pilli, Satyananda Kishore; Summers, Kodi; Chidambaram, Dev

2015-06-07

This study demonstrates solar driven oxidation of hydrazine hydrate and the simultaneous production of hydrogen and electricity in photoelectrochemical cells and photofuel cells, respectively, using a visible light active molybdenum doped BiVO4 photoelectrode. The developed photoelectrodes exhibited tremendous efficiency towards anodic oxidation of hydrous hydrazine with continuous and stable hydrogen evolution at the Pt cathode under benign pH and zero bias conditions. Significantly, the photofuel cell containing hydrazine hydrate fuel has generated electricity with a high open circuit potential of 0.8 V. The presence of bicarbonate ions in the electrolyte has played a significant role in enhancing the kinetics of photoelectrochemical oxidation of hydrazine and improved the hydrogen and electricity generation efficiency thus avoiding the integration of an oxidation electrocatalyst. In addition, molybdenum doped BiVO4 as a possible photoelectrochemical hydrazine sensor has been investigated and the electrode photocurrent was found to be linearly dependent on the concentration of the hydrazine hydrate in the range of 20-90 mM with a correlation coefficient of 0.9936.

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.

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.

Adsorption of Kinetic Hydrate Inhibitors on Growing Surfaces: A Molecular Dynamics Study.

PubMed

Yagasaki, Takuma; Matsumoto, Masakazu; Tanaka, Hideki

2018-04-05

We investigate the mechanism of a typical kinetic hydrate inhibitor (KHI), polyvinylcaprolactam (PVCap), which has been applied to prevent hydrate plugs from forming in gas pipe lines, using molecular dynamics simulations of crystal growth of ethylene oxide hydrate. Water-soluble ethylene oxide is chosen as a guest species to avoid problems associated with the presence of the gas phase in the simulation cell such as slow crystal growth. A PVCap dodecamer adsorbs irreversibly on the hydrate surface which grows at supercooling of 3 K when the hydrophobic part of two pendent groups are trapped in open cages at the surface. The amide hydrogen bonds make no contribution to the adsorption. PVCap can adsorb on various crystallographic planes of sI hydrate. This is in contrast to antifreeze proteins, each of which prefers a specific plane of ice. The trapped PVCap gives rise to necessarily the concave surface of the hydrate. The crystal growth rate decreases with increasing surface curvature, indicating that the inhibition by PVCap is explained by the Gibbs-Thomson effect.

Roles of Acetone and Diacetone Alcohol in Coordination and Dissociation Reactions of Uranyl Complexes

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

Rios, Daniel; Schoendorff, George E.; Van Stipdonk, Michael J.

2012-12-03

Combined collision-induced dissociation mass-spectrometry experiments and DFT calculations were employed to elucidate the molecular structure of "hypercoordinated" species and the energetics of water-elimination reactions of uranyl acetone complexes observed in earlier work (Rios, D.; Rutkowski, P. X.; Van Stipdonk, M. J.; Gibson, J. K. Inorg. Chem. 2011, 50, 4781). It is shown that the "hypercoordinated" species contain diacetone alcohol ligands bonded in either bidentate or monodentate fashion, which are indistinguishable from (acetone)2 in mass spectrometry. Calculations confirm that four diacetone ligands can form stable complexes, but that the effective number of atoms coordinating with uranium in the equatorial plane doesmore » not exceed five. Diacetone alcohol ligands are shown to form mesityl oxide ligands and alkoxide species through the elimination of water, providing an explanation for the observed water-elimination reactions.« less

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.

Morin Hydrate Mitigates Cisplatin-Induced Renal and Hepatic Injury by Impeding Oxidative/Nitrosative Stress and Inflammation in Mice.

PubMed

K V, Athira; Madhana, Rajaram Mohanrao; Kasala, Eshvendar Reddy; Samudrala, Pavan Kumar; Lahkar, Mangala; Gogoi, Ranadeep

2016-12-01

Cisplatin is a widely used chemotherapeutic drug; however, it induces damage on kidney and liver at clinically effective higher doses. Morin hydrate possesses antioxidant, anti-inflammatory, and anticancer properties. Therefore, we aimed to investigate the effects of morin hydrate (50 and 100 mg/kg, orally) against the renohepatic toxicity induced by a high dose of cisplatin (20 mg/kg, intraperitoneally). Renal and hepatic function, oxidative/nitrosative stress, and inflammatory markers along with histopathology were evaluated. Morin hydrate ameliorated cisplatin-induced renohepatic toxicity significantly at 100 mg/kg as evidenced from the significant reversal of cisplatin-induced body weight loss, mortality, functional and structural alterations of kidney, and liver. The protective role offered by morin hydrate against cisplatin-induced renohepatic toxicity is by virtue of its free radical scavenging property, thereby abating the depletion of cellular antioxidant defense components and through modulation of inflammatory cytokines. We speculate morin hydrate as a protective candidate against renohepatic toxicity of cisplatin. © 2016 Wiley Periodicals, Inc.

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.

Cross Directorate Proposal: Nanostructured Materials for Munitions and Propellants-Production, Modeling, and Characterization

DTIC Science & Technology

2016-07-15

towards hydration and decomposition along with probing their hydration mechanisms, we are now exploring processing and deposition effects for this...oxidizer films and tested for their reactivity. Hydration Mechanism for HI3O8 → HIO3 Previous efforts by our group investigating the hydration ...mechanism of I2O5 → HI3O8 reflected that the hydration mechanism proceeded through a nucleation and growth process followed by a diffusion limited

Method of forming oxide coatings. [for solar collector heating panels

NASA Technical Reports Server (NTRS)

Mcdonald, G. E. (Inventor)

1983-01-01

This invention is concerned with an improved plating process for covering a substrate with a black metal oxide film. The invention is particularly directed to making a heating panel for a solar collector. A compound is electrodeposited from an aqueous solution containing cobalt metal salts onto a metal substrate. This compound is converted during plating into a black, highly absorbing oxide coating which contains hydrated oxides. This is achieved by the inclusion of an oxidizing agent in the plating bath. The inclusion of an oxidizing agent in the plating bath is contrary to standard electroplating practice. The hydrated oxides are converted to oxides by treatment in a hot bath, such as boiling water. An oxidizing agent may be added to the hot liquid treating bath.

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.

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.

Polyethylene oxide hydration in grafted layers

NASA Astrophysics Data System (ADS)

Dormidontova, Elena; Wang, Zilu

Hydration of water soluble polymers is one of the key-factors defining their conformation and properties, similar to biopolymers. Polyethylene oxide (PEO) is one of the most important biomedical-applications polymers and is known for its reverse temperature solubility due to hydrogen bonding with water. As in many practical applications PEO chains are grafted to surfaces, e.g. of nanoparticles or planar surfaces, it is important to understand PEO hydration in such grafted layers. Using atomistic molecular dynamic simulations we investigate the details of molecular conformation and hydration of PEO end-grafted to gold surfaces. We analyze polymer and water density distribution as a function of distance from the surface for different grafting densities. Based on a detailed analysis of hydrogen bonding between polymer and water in grafted PEO layers, we will discuss the extent of PEO hydration and its implication for polymer conformation, mobility and layer properties. This research is supported by NSF (DMR-1410928).

Influence of uranyl speciation and iron oxides on uranium biogeochemical redox reactions

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

Stewart, B.D.; Amos, R.T.; Nico, P.S.

2010-03-15

Uranium is a pollutant of concern to both human and ecosystem health. Uranium's redox state often dictates its partitioning between the aqueous- and solid-phases, and thus controls its dissolved concentration and, coupled with groundwater flow, its migration within the environment. In anaerobic environments, the more oxidized and mobile form of uranium (UO{sub 2}{sup 2+} and associated species) may be reduced, directly or indirectly, by microorganisms to U(IV) with subsequent precipitation of UO{sub 2}. However, various factors within soils and sediments may limit biological reduction of U(VI), inclusive of alterations in U(VI) speciation and competitive electron acceptors. Here we elucidate themore » impact of U(VI) speciation on the extent and rate of reduction with specific emphasis on speciation changes induced by dissolved Ca, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite and hematite) varying in free energies of formation on U reduction. The amount of uranium removed from solution during 100 h of incubation with S. putrefaciens was 77% with no Ca or ferrihydrite present but only 24% (with ferrihydrite) and 14% (no ferrihydrite) were removed for systems with 0.8 mM Ca. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Dissimilatory reduction of Fe(III) and U(VI) can proceed through different enzyme pathways, even within a single organism, thus providing a potential second means by which Fe(III) bearing minerals may impact U(VI) reduction. We quantify rate coefficients for simultaneous dissimilatory reduction of Fe(III) and U(VI) in systems varying in Ca concentration (0 to 0.8 mM), and using a mathematical construct implemented with the reactive transport code MIN3P, we reveal the predominant influence of uranyl speciation, specifically the formation of uranyl-calcium-carbonato complexes, and ferrihydrite on the rate and extent of uranium reduction in complex geochemical systems.« less

Ruthenium Nanoparticles Mediated Electrocatalytic Reduction of UO22+ Ions for Its Rapid and Sensitive Detection in Natural Waters.

PubMed

Gupta, Ruma; Sundararajan, Mahesh; Gamare, Jayashree S

2017-08-01

Reduction of UO 2 2+ ions to U 4+ ions is difficult due to involvement of two axially bonded oxygen atoms, and often requires a catalyst to lower the activation barrier. The noble metal nanoparticles (NPs) exhibit high electrocatalytic activity, and could be employed for the sensitive and rapid quantifications of U0 2 2+ ions in the aqueous matrix. Therefore, the Pd, Ru, and Rh NPs decorated glassy carbon electrode were examined for their efficacy toward electrocatalytic reduction of UO 2 2+ ions and observed that Ru NPs mediate efficiently the electro-reduction of UO 2 2+ ions. The mechanism of the electroreduction of UO 2 2+ by the RuNPs/GC was studied using density functional theory calculations which pointed different approach of 5f metal ions electroreduction unlike 4p metal ions such as As(III). RuNP decorated on the glassy carbon would be hydrated, which in turn assist to adsorb the uranyl sulfates through hydrogen bonding thus facilitated electro-reduction. Differential pulse voltammetric (DPV) technique, was used for rapid and sensitive quantification of UO 2 2+ ions. The RuNPs/GC based DPV technique could be used to determine the concentration of uranyl in a few minutes with a detection limit of 1.95 ppb. The RuNPs/GC based DPV was evaluated for its analytical performance using seawater as well lake water and groundwater spiked with known amounts of UO 2 2+ .

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.

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.

Energetics of alkali and alkaline earth ion-exchanged zeolite A

DOE PAGES

Sun, Hui; Wu, Di; Liu, Kefeng; ...

2016-06-30

Alkali and alkaline earth ion-exchanged zeolite A samples were synthesized in aqueous exchange media. They were thoroughly studied by powder X-ray diffraction (XRD), electron microprobe (EMPA), thermogravimetric analysis and differential scanning calorimetry (TG-DSC), and high temperature oxide melt solution calorimetry. The hydration energetics and enthalpies of formation of these zeolite A materials from constituent oxides were determined. Specifically, the hydration level of zeolite A has a linear dependence on the average ionic potential ( Z/r) of the cation, from 0.894 (Rb-A) to 1.317 per TO 2 (Mg-A). The formation enthalpies from oxides (25 °C) range from –93.71 ± 1.77 (K-A)more » to –48.02 ± 1.85 kJ/mol per TO 2 (Li-A) for hydrated alkali ion-exchanged zeolite A, and from –47.99 ± 1.20 (Ba-A) to –26.41 ± 1.71 kJ/mol per TO 2 (Mg-A) for hydrated alkaline earth ion-exchanged zeolite A. As a result, the formation enthalpy from oxides generally becomes less exothermic as Z/r increases, but a distinct difference in slope is observed between the alkali and the alkaline earth series.« less

Origins of saccharide-dependent hydration at aluminate, silicate, and aluminosilicate surfaces.

PubMed

Smith, Benjamin J; Rawal, Aditya; Funkhouser, Gary P; Roberts, Lawrence R; Gupta, Vijay; Israelachvili, Jacob N; Chmelka, Bradley F

2011-05-31

Sugar molecules adsorbed at hydrated inorganic oxide surfaces occur ubiquitously in nature and in technologically important materials and processes, including marine biomineralization, cement hydration, corrosion inhibition, bioadhesion, and bone resorption. Among these examples, surprisingly diverse hydration behaviors are observed for oxides in the presence of saccharides with closely related compositions and structures. Glucose, sucrose, and maltodextrin, for example, exhibit significant differences in their adsorption selectivities and alkaline reaction properties on hydrating aluminate, silicate, and aluminosilicate surfaces that are shown to be due to the molecular architectures of the saccharides. Solid-state (1)H, (13)C, (29)Si, and (27)Al nuclear magnetic resonance (NMR) spectroscopy measurements, including at very high magnetic fields (19 T), distinguish and quantify the different molecular species, their chemical transformations, and their site-specific adsorption on different aluminate and silicate moieties. Two-dimensional NMR results establish nonselective adsorption of glucose degradation products containing carboxylic acids on both hydrated silicates and aluminates. In contrast, sucrose adsorbs intact at hydrated silicate sites and selectively at anhydrous, but not hydrated, aluminate moieties. Quantitative surface force measurements establish that sucrose adsorbs strongly as multilayers on hydrated aluminosilicate surfaces. The molecular structures and physicochemical properties of the saccharides and their degradation species correlate well with their adsorption behaviors. The results explain the dramatically different effects that small amounts of different types of sugars have on the rates at which aluminate, silicate, and aluminosilicate species hydrate, with important implications for diverse materials and applications.

Structure and thermodynamic stability of UTa 3 O 10 , a U( v )-bearing compound

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

Guo, Xiaofeng; Lipp, Christian; Tiferet, Eitan

Heating a mixture of uranyl(VI) nitrate and tantalum(V) oxide in the molar ratio of 2 : 3 to 1400 °C resulted in the formation of a new compound, UTa 3O 10. The honey colored to yellow brown crystals of UTa 3O 10 crystallize in an orthorhombic structure with the space group Fddd (no. 70), lattice parameters a = 7.3947(1), b = 12.7599(2), c = 15.8156(2) Å, and Z = 8. Vertex sharing [TaO 6] 7- octahedra of two crystallographically distinct Ta cations form a three dimensional tantalate framework. Within this framework, six membered rings of [TaO 6] 7- octahedra aremore » formed within the (001) plane. The center of these rings is occupied by the uranyl cations [UO 2] +, with an oxidation state of +5 for uranium. The pentavalence of U and Ta was confirmed by X-ray photoelectron spectroscopy and X-ray adsorption spectroscopy. The enthalpy of formation of UTa 3O 10 from Ta 2O 5, β-U 3O 7, and U 3O 8 has been determined to be 13.1 ± 18.1 kJ mol -1 using high temperature oxide melt solution calorimetry with sodium molybdate as the solvent at 700 °C. The close to zero enthalpy of formation of UTa 3O 10 can be explained by closely balanced structural stabilizing and destabilizing factors, which may also apply to other UM 3O 10 compounds.« less

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

Unexpected Interactions of the Cyanobacterial Metallothionein SmtA with Uranium.

PubMed

Acharya, Celin; Blindauer, Claudia A

2016-02-15

Molecules for remediating or recovering uranium from contaminated environmental resources are of high current interest, with protein-based ligands coming into focus recently. Metallothioneins either bind or redox-silence a range of heavy metals, conferring protection against metal stress in many organisms. Here, we report that the cyanobacterial metallothionein SmtA competes with carbonate for uranyl binding, leading to formation of heterometallic (UO2)(n)Zn4SmtA species, without thiol oxidation, zinc loss, or compromising secondary or tertiary structure of SmtA. In turn, only metalated and folded SmtA species were found to be capable of uranyl binding. (1)H NMR studies and molecular modeling identified Glu34/Asp38 and Glu12/C-terminus as likely adventitious, but surprisingly strong, bidentate binding sites. While it is unlikely that these interactions correspond to an evolved biological function of this metallothionein, their occurrence may offer new possibilities for designing novel multipurpose bacterial metallothioneins with dual ability to sequester both soft metal ions including Cu(+), Zn(2+), Cd(2+), Hg(2+), and Pb(2+) and hard, high-oxidation state heavy metals such as U(VI). The concomitant protection from the chemical toxicity of uranium may be valuable for the development of bacterial strains for bio-remediation.

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.

Spectroscopic And Electrochemical Studies Of Electrochromic Hydrated Nickel Oxide Films

NASA Astrophysics Data System (ADS)

Yu, P. C.; Nazri, G.; Lampert, C. M.

1986-09-01

The electrochrcrnic properties of hydrated nickel oxide thin films electrochemically deposited by anodization onto doped tin oxide-coated glass have been studied by transmittance measurements, cyclic voltammetry, Fourier-transform infrared spectroscopy, and ion-backscattering spectrometry. The spectral transmittance is reported for films switched in both the bleached and colored states. The photopic transmittance (Tp) can be switched from T (bleached) = 0.77 to T (colored) = 0.21, and the solar transmittance (Ts) can be switched from Ts(bleached) = 0.73 to TS (colored) = 0.35. Also reported is the near-infrared transmittance (TNIR)which was found to switch fran T N,IR (bleached) = 0.72 to TNIR (colored) = 0.55. The bleached condition is noted to have very low solar absorption in both the visible and solar regions. Ion-backscattering spectrometry was performed on the hydrated nickel oxide film, yielding a camposition of Ni01.0 (dehydrated) and a film thickness of 125 A. Cyclic voltammetry showed that, for films in the bleached or colored state, the reversible reaction is Ni(0H), = NiOOH + H+ + e . Voltammnetry also showed that the switching of the film is controlled by the diffusion or protons, where OH plays a role in the reaction mechanism. Analysis of the hydrated nickel-oxide thin films by Fourier-transform infrared spectroscopy revealed that both the bleached and colored states contain lattice water and hydroxyl groups. The surface hydroxyl groups play an important role in the coloration and bleaching of the anodically deposited nickel oxide thin films.

Characterization of un-hydrated and hydrated BioAggregate™ and MTA Angelus™.

PubMed

Camilleri, J; Sorrentino, F; Damidot, D

2015-04-01

BioAggregate™ is a novel material introduced for use as a root-end filling material. It is tricalcium silicate-based, free of aluminium and uses tantalum oxide as radiopacifier. BioAggregate contains additives to enhance the material performance. The purpose of this research was to characterize the un-hydrated and hydrated forms of BioAggregate using a combination of techniques, verify whether the additives if present affect the properties of the set material and compare these properties to those of MTA Angelus™. Un-hydrated and hydrated BioAggregate and MTA Angelus were assessed. Un-hydrated cement was tested for chemical composition, specific surface area, mineralogy and kinetics of hydration. The set material was investigated for mineralogy, microstructure and bioactivity. Scanning electron microscopy, X-ray energy dispersive spectroscopic analysis, X-ray fluorescence spectroscopy, X-ray diffraction and isothermal calorimetry were employed. The specific surface area was investigated using a gas adsorption method with nitrogen as the probe. BioAggregate was composed of tricalcium silicate, tantalum oxide, calcium phosphate and silicon dioxide and was free of aluminium. On hydration, the tricalcium silicate produced calcium silicate hydrate and calcium hydroxide. The former was deposited around the cement grains, while the latter reacted with the silicon dioxide to form additional calcium silicate hydrate. This resulted in reduction of calcium hydroxide in the aged cement. MTA Angelus reacted in a similar fashion; however, since it contained no additives, the calcium hydroxide was still present in the aged cement. Bioactivity was demonstrated by deposition of hydroxyapatite. BioAggregate exhibited a high specific surface area. Nevertheless, the reactivity determined by isothermal calorimetry appeared to be slow compared to MTA Angelus. The tantalum oxide as opposed to bismuth oxide was inert, and tantalum was not leached in solution. BioAggregate exhibited high calcium ion release early, which was maintained over the 28-day period as opposed to MTA Angelus, which demonstrated low early calcium ion release which increased as the material aged. The mineralogical composition of BioAggregate was different to MTA Angelus. As opposed to MTA Angelus, BioAggregate did not contain aluminium and contained additives such as calcium phosphate and silicon dioxide. As a consequence, BioAggregate reacted more slowly and formation of calcium hydroxide and leaching of calcium ions in solution were not evident as the material aged. The additives in BioAggregate modify the kinetics and the end products of hydration. Although newer generation tricalcium silicate-based materials contain similar constituents to MTA, they do not undergo the same setting reactions, and thus, their clinical performance will not be comparable to that of MTA.

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

The geochemistry of water near a surficial organic-rich uranium deposit, northeastern Washington State, U.S.A.

USGS Publications Warehouse

Zielinski, R.A.; Otton, J.K.; Wanty, R.B.; Pierson, C.T.

1987-01-01

The chemistry of three stream, three spring and six near-surface waters in the vicinity of a Holocene organic-rich uranium deposit is described, with particular emphasis on the chemistry of U. Results characterize the solution behavior of uranium as U-bearing water interacts with relatively undecomposed, surficial organic matter. Of the measured major and trace chemical species, only U is consistently highly enriched (17-318 ppb) relative to reported values for regional waters, or to literature values for waters in largely granitic terrains. R-mode factor analysis of the chemical data suggests that most U is present in a soluble form, but that some U is also associated with fine suspended particulates of clay, organic matter, or hydrous oxides. Calculations that apply thermodynamic data to predict U speciation in solution indicate the relative importance of uranyl carbonate and uranyl phosphate complexes. Analysis of more finely filtered samples (0.05 ??m vs. 0.45 ??m), and direct radiographic observations using fission-track detectors suspended in the waters indicate the presence of some uraniferous particulate matter. Application of existing thermodynamic data for uranous- and uranyl-bearing minerals indicates that all waters are undersaturated with U minerals as long as ambient Eh ??? +0.1 v. If coexisting surface and near-surface waters are sufficiently oxidizing, initial fixation of U in the deposit should be by a mechanism of adsorption. Alternatively, more reducing conditions may prevail in deeper pore waters of the organic-rich host sediments, perhaps leading to direct precipitation or diagenetic formation of U4+ minerals. A 234U 238U alpha activity ratio of 1.08 ?? 0.02 in a spring issuing from a hillslope above the deposit suggests a relatively soluble source of U. In contrast, higher activity ratios of 234U 238U (??? 1.3) in waters in contact with the uraniferous valley-fill sediments suggest differences in the nature of interaction between groundwater and the local, U-rich source rocks. ?? 1987.

Energetics of sodium-calcium exchanged zeolite A.

PubMed

Sun, H; Wu, D; Guo, X; Shen, B; Navrotsky, A

2015-05-07

A series of calcium-exchanged zeolite A samples with different degrees of exchange were prepared. They were characterized by powder X-ray diffraction (XRD) and differential scanning calorimetry (DSC). High temperature oxide melt drop solution calorimetry measured the formation enthalpies of hydrated zeolites CaNa-A from constituent oxides. The water content is a linear function of the degree of exchange, ranging from 20.54% for Na-A to 23.77% for 97.9% CaNa-A. The enthalpies of formation (from oxides) at 25 °C are -74.50 ± 1.21 kJ mol(-1) TO2 for hydrated zeolite Na-A and -30.79 ± 1.64 kJ mol(-1) TO2 for hydrated zeolite 97.9% CaNa-A. Dehydration enthalpies obtained from differential scanning calorimetry are 32.0 kJ mol(-1) H2O for hydrated zeolite Na-A and 20.5 kJ mol(-1) H2O for hydrated zeolite 97.9% CaNa-A. Enthalpies of formation of Ca-exchanged zeolites A are less exothermic than for zeolite Na-A. A linear relationship between the formation enthalpy and the extent of calcium substitution was observed. The energetic effect of Ca-exchange on zeolite A is discussed with an emphasis on the complex interactions between the zeolite framework, cations, and water.

From Black Hole to Hydrate Hole: Gas hydrates, authigenic carbonates and vent biota as indicators of fluid migration at pockmark sites of the Northern Congo Fan

NASA Astrophysics Data System (ADS)

Kasten, S.; Schneider, R.; Spiess, V.; Cruise Participants Of M56b

2003-04-01

A recent high-resolution seismic, echosounder and video survey combined with detailed geological and geochemical sampling of pockmark sites on the Northern Congo Fan was carried out with RV Meteor in November/December 2002 in the frame of the project "CONGO" (BMBF/BEO "Geotechnologien"). These investigations revealed the extensive occurrence of surface and sub-surface gas hydrates as well as characteristic features of fluid venting such as clams (Calyptogena), tube worms (Pogonophera) and huge amounts of authigenic carbonates. In a first approach the patchyness in the occurrence of these features was mapped in relation to pockmark structure and seismic reflectors. Detailed sampling of three pockmarks by gravity corer showed that gas hydrates are present at and close to the sediment surface and often occur as several distinct layers and/or veins intercalated with hemipelagic muds. The depth of the upper boundary of these hydrate-bearing sediments increases from the center towards the edge of the pockmark structures. Pore water concentration profiles of sulfate and methane document the process of anaerobic methane oxidation above the hydrate-bearing layers. For those cores which contained several gas hydrate layers preliminary pore water profiles suggest the occurrence of more than one zone of anaerobic methane oxidation. Authigenic carbonates are found in high abundance, irregularly distributed within the pockmarks close to the sediment surface. These carbonates occur in a wide variety with respect to size, shape, structure and mineralogy. Their formation is associated with high amounts of bicarbonate released by the process of anaerobic methane oxidation. In the gravity cores authigenic carbonates are always present above hydrate-bearing sections. However, the quantities and characteristics of these authigenic minerals in relation to venting and microbial activity as well as to gas hydrate dissociation are not clear yet. Unraveling this relationship will be a major target of further investigation. By means of detailed studies of the sedimentary solid-phase, authigenic carbonates, clam layers and molecular biomarkers we will also try to reconstruct the history of venting and the dynamics of gas hydrate formation and decomposition in the Northern Congo fan area.

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

PROCESS FOR RECOVERY OF URANIUM VALUES FROM IMPURE SOLUTIONS THEREOF

DOEpatents

Kilner, S.B.

1959-11-01

A process is presented for the recovery of uraninm values from impure solutions which are obtained, for example, by washing residual uranium salt or uranium metal deposits from stainless steel surfaces using an aqueous or certain acidic aqueous solutions. The solutions include uranyl and oxidized iron, chromium, nickel, and copper ions and may contain manganese, zinc, and silver ions. In accordance with one procedure. the uranyl ions are reduced to the uranous state, and the impurity ions are complexed with cyanide under acidic conditions. The solution is then treated with ammonium hydroxide or alkali metal hydroxide to precipitate uranous hydroxide away from the complexed impurity ions in the solution. Alternatively, an excess of alkali metal cyanide is added to the reduced solution until the solution becomes sufficiently alkaline for the uranons hydroxide to precipitate. An essential feature in operating the process is in maintaining the pH of the solution sufficiently acid during the complexing operation to prevent the precipitation of the impurity metal hydroxides.

Oxidation Dynamics of Methionine with Singlet Oxygen: Effects of Methionine Ionization and Microsolvation.

PubMed

Liu, Fangwei; Liu, Jianbo

2015-06-25

We report an in-depth study on the gas-phase reactions of singlet O2[a(1)Δg] with methionine (Met) at different ionization and hydration states (including deprotonated [Met - H](-), hydrated deprotonated [Met - H](-)(H2O)1,2, and hydrated protonated MetH(+)(H2O)1,2), using guided-ion-beam scattering mass spectrometry. The measurements include the effects of collision energy (Ecol) on reaction cross sections over a center-of-mass Ecol range from 0.05 to 1.0 eV. The aim of this study is to probe the influences of Met ionization and hydration on its oxidation mechanism and dynamics. Density functional theory calculations, Rice-Ramsperger-Kassel-Marcus modeling, and quasi-classical, direct dynamics trajectory simulations were performed to examine the properties of various complexes and transition states that might be important along reaction coordinates, probe reaction potential energy surfaces, and to establish the atomic-level mechanism for the Met oxidation process. No oxidation products were observed for the reaction of [Met - H](-) with (1)O2 due to the high-energy barriers located in the product channels for this system. However, this nonreactive property was altered by the microsolvation of [Met - H](-); as a result, hydroperoxides were captured as the oxidation products for [Met - H](-)(H2O)1,2 + (1)O2. For the reaction of MetH(+)(H2O)1,2 + (1)O2, besides formation of hydroperoxides, an H2O2 elimination channel was observed. The latter channel is similar to what was found in the reaction of dehydrated MetH(+) with (1)O2 (J. Phys. Chem. B 2011, 115, 2671). The reactions of hydrated protonated and deprotonated Met are all inhibited by Ecol, becoming negligible at Ecol ≥ 0.5 eV. The kinetic and dynamical consequences of microsolvation on Met oxidation and their biological implications are discussed.

Induction of Inducible Nitric Oxide Synthase by Lipopolysaccharide and the Influences of Cell Volume Changes, Stress Hormones and Oxidative Stress on Nitric Oxide Efflux from the Perfused Liver of Air-Breathing Catfish, Heteropneustes fossilis

PubMed Central

Choudhury, Mahua G.; Saha, Nirmalendu

2016-01-01

The air-breathing singhi catfish (Heteropneustes fossilis) is frequently being challenged by bacterial contaminants, and different environmental insults like osmotic, hyper-ammonia, dehydration and oxidative stresses in its natural habitats throughout the year. The main objectives of the present investigation were to determine (a) the possible induction of inducible nitric oxide synthase (iNOS) gene with enhanced production of nitric oxide (NO) by intra-peritoneal injection of lipopolysaccharide (LPS) (a bacterial endotoxin), and (b) to determine the effects of hepatic cell volume changes due to anisotonicity or by infusion of certain metabolites, stress hormones and by induction of oxidative stress on production of NO from the iNOS-induced perfused liver of singhi catfish. Intra-peritoneal injection of LPS led to induction of iNOS gene and localized tissue specific expression of iNOS enzyme with more production and accumulation of NO in different tissues of singhi catfish. Further, changes of hydration status/cell volume, caused either by anisotonicity or by infusion of certain metabolites such as glutamine plus glycine and adenosine, affected the NO production from the perfused liver of iNOS-induced singhi catfish. In general, increase of hydration status/cell swelling due to hypotonicity caused decrease, and decrease of hydration status/cell shrinkage due to hypertonicity caused increase of NO efflux from the perfused liver, thus suggesting that changes in hydration status/cell volume of hepatic cells serve as a potent modulator for regulating the NO production. Significant increase of NO efflux from the perfused liver was also observed while infusing the liver with stress hormones like epinephrine and norepinephrine, accompanied with decrease of hydration status/cell volume of hepatic cells. Further, oxidative stress, caused due to infusion of t-butyl hydroperoxide and hydrogen peroxide separately, in the perfused liver of singhi catfish, resulted in significant increase of NO efflux accompanied with decrease of hydration status/cell volume of hepatic cells. However, the reasons for these cell volume-sensitive changes of NO efflux from the liver of singhi catfish are not fully understood with the available data. Nonetheless, enhanced or decreased production of NO from the perfused liver under osmotic stress, in presence of stress hormones and oxidative stress reflected its potential role in cellular homeostasis and also for better adaptations under environmental challenges. This is the first report of osmosensitive and oxidative stress-induced changes of NO production and efflux from the liver of any teleosts. Further, the level of expression of iNOS in this singhi catfish could also serve as an important indicator to determine the pathological status of the external environment. PMID:26950213

Induction of Inducible Nitric Oxide Synthase by Lipopolysaccharide and the Influences of Cell Volume Changes, Stress Hormones and Oxidative Stress on Nitric Oxide Efflux from the Perfused Liver of Air-Breathing Catfish, Heteropneustes fossilis.

PubMed

Choudhury, Mahua G; Saha, Nirmalendu

2016-01-01

The air-breathing singhi catfish (Heteropneustes fossilis) is frequently being challenged by bacterial contaminants, and different environmental insults like osmotic, hyper-ammonia, dehydration and oxidative stresses in its natural habitats throughout the year. The main objectives of the present investigation were to determine (a) the possible induction of inducible nitric oxide synthase (iNOS) gene with enhanced production of nitric oxide (NO) by intra-peritoneal injection of lipopolysaccharide (LPS) (a bacterial endotoxin), and (b) to determine the effects of hepatic cell volume changes due to anisotonicity or by infusion of certain metabolites, stress hormones and by induction of oxidative stress on production of NO from the iNOS-induced perfused liver of singhi catfish. Intra-peritoneal injection of LPS led to induction of iNOS gene and localized tissue specific expression of iNOS enzyme with more production and accumulation of NO in different tissues of singhi catfish. Further, changes of hydration status/cell volume, caused either by anisotonicity or by infusion of certain metabolites such as glutamine plus glycine and adenosine, affected the NO production from the perfused liver of iNOS-induced singhi catfish. In general, increase of hydration status/cell swelling due to hypotonicity caused decrease, and decrease of hydration status/cell shrinkage due to hypertonicity caused increase of NO efflux from the perfused liver, thus suggesting that changes in hydration status/cell volume of hepatic cells serve as a potent modulator for regulating the NO production. Significant increase of NO efflux from the perfused liver was also observed while infusing the liver with stress hormones like epinephrine and norepinephrine, accompanied with decrease of hydration status/cell volume of hepatic cells. Further, oxidative stress, caused due to infusion of t-butyl hydroperoxide and hydrogen peroxide separately, in the perfused liver of singhi catfish, resulted in significant increase of NO efflux accompanied with decrease of hydration status/cell volume of hepatic cells. However, the reasons for these cell volume-sensitive changes of NO efflux from the liver of singhi catfish are not fully understood with the available data. Nonetheless, enhanced or decreased production of NO from the perfused liver under osmotic stress, in presence of stress hormones and oxidative stress reflected its potential role in cellular homeostasis and also for better adaptations under environmental challenges. This is the first report of osmosensitive and oxidative stress-induced changes of NO production and efflux from the liver of any teleosts. Further, the level of expression of iNOS in this singhi catfish could also serve as an important indicator to determine the pathological status of the external environment.

Structural determination of individual chemical species in a mixed system by iterative transformation factor analysis-based X-ray absorption spectroscopy combined with UV-visible absorption and quantum chemical calculation.

PubMed

Ikeda, Atsushi; Hennig, Christoph; Rossberg, André; Tsushima, Satoru; Scheinost, Andreas C; Bernhard, Gert

2008-02-15

A multitechnique approach using extended X-ray absorption fine structure (EXAFS) spectroscopy based on iterative transformation factor analysis (ITFA), UV-visible absorption spectroscopy, and density functional theory (DFT) calculations has been performed in order to investigate the speciation of uranium(VI) nitrate species in acetonitrile and to identify the complex structure of individual species in the system. UV-visible spectral titration suggests that there are four different species in the system, that is, pure solvated species, mono-, di-, and trinitrate species. The pure EXAFS spectra of these individual species are extracted by ITFA from the measured spectral mixtures on the basis of the speciation distribution profile calculated from the UV-visible data. Data analysis of the extracted EXAFS spectra, with the help of DFT calculations, reveals the most probable complex structures of the individual species. The pure solvated species corresponds to a uranyl hydrate complex with an equatorial coordination number (CNeq) of 5, [UO2(H2O)5]2+. Nitrate ions tend to coordinate to the uranyl(VI) ion in a bidentate fashion rather than a unidentate one in acetonitrile for all the nitrate species. The mononitrate species forms the complex of [UO2(H2O)3NO3]+ with a CNeq value of 5, while the di- and trinitrate species have a CNeq value of 6, corresponding to [UO2(H2O)2(NO3)2]0 (D2h) and [UO2(NO3)3]- (D3h), respectively.

Mesoporous metal oxide microsphere electrode compositions and their methods of making

DOEpatents

Paranthaman, Mariappan Parans; Liu, Hansan; Brown, Gilbert M.; Sun, Xiao-Guang; Bi, Zhonghe

2016-12-06

Compositions and methods of making are provided for mesoporous metal oxide microspheres electrodes. The mesoporous metal oxide microsphere compositions comprise (a) microspheres with an average diameter between 200 nanometers (nm) and 10 micrometers (.mu.m); (b) mesopores on the surface and interior of the microspheres, wherein the mesopores have an average diameter between 1 nm and 50 nm and the microspheres have a surface area between 50 m.sup.2/g and 500 m.sup.2/g. The methods of making comprise forming composite powders. The methods may also comprise refluxing the composite powders in a basic solution to form an etched powder, washing the etched powder with an acid to form a hydrated metal oxide, and heat-treating the hydrated metal oxide to form mesoporous metal oxide microspheres.

Evaluation of the thermodynamic properties of hydrated metal oxide nanoparticles by INS techniques

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

Spencer, Elinor; Ross, Dr. Nancy; Parker, Stewart F.

2013-01-01

In this contribution we will present a detailed methodology for the elucidation of the following aspects of the thermodynamic properties of hydrated metal oxide nanoparticles from high-resolution, low-temperature inelastic neutron scattering (INS) data: (i) the isochoric heat capacity and entropy of the hydration layers both chemi- and physisorbed to the particle surface; (ii) the magnetic contribution to the heat capacity of the nanoparticles. This will include the calculation of the vibrational density of states (VDOS) from the raw INS spectra, and the subsequent extraction of the thermodynamic data from the VDOS. This technique will be described in terms of amore » worked example namely, cobalt oxide (Co3O4 and CoO). To complement this evaluation of the physical properties of metal oxide nanoparticle systems, we will emphasise the importance of high-resolution, high-energy INS for the determination of the structure and dynamics of the water species, namely molecular (H2O) and dissociated water (OH, hydroxyl), confined to the oxide surfaces. For this component of the chapter we will focus on INS investigations of hydrated isostructural rutile (a-TiO2) and cassiterite (SnO2) nanoparticles. We will complete this discussion of nanoparticle analysis by including an appraisal of the INS instrumentation employed in such studies with particular focus on TOSCA [ISIS, Rutherford Appleton Laboratory (RAL), U.K.] and the newly developed spectrometer SEQUOIA [SNS, Oak Ridge National Laboratory (ORNL), U.S.A].« less

Uranium(VI) Scavenging by Amorphous Iron Phosphate Encrusting Sphaerotilus natans Filaments.

PubMed

Seder-Colomina, Marina; Morin, Guillaume; Brest, Jessica; Ona-Nguema, Georges; Gordien, Nilka; Pernelle, Jean-Jacques; Banerjee, Dipanjan; Mathon, Olivier; Esposito, Giovanni; van Hullebusch, Eric D

2015-12-15

U(VI) sorption to iron oxyhydroxides, precipitation of phosphate minerals, as well as biosorption on bacterial biomass are among the most reported processes able to scavenge U(VI) under oxidizing conditions. Although phosphates significantly influence bacterially mediated as well as iron oxyhydroxide mediated scavenging of uranium, the sorption or coprecipitation of U(VI) with poorly crystalline nanosized iron phosphates has been scarcely documented, especially in the presence of microorganisms. Here we show that dissolved U(VI) can be bound to amorphous iron phosphate during their deposition on Sphaerotilus natans filamentous bacteria. Uranium LIII-edge EXAFS analysis reveals that the adsorbed uranyl ions share an equatorial oxygen atom with a phosphate tetrahedron of the amorphous iron phosphate, with a characteristic U-P distance of 3.6 Å. In addition, the uranyl ions are connected to FeO6 octahedra with U-Fe distances at ~3.4 Å and at ~4.0 Å. The shortest U-Fe distance corresponds to a bidentate edge-sharing complex often reported for uranyl adsorption onto iron oxyhydroxides, whereas the longest U-Fe and U-P distances can be interpreted as a bidentate corner-sharing complex, in which two adjacent equatorial oxygen atoms are shared with the vertices of a FeO6 octahedron and of a phosphate tetrahedron. Furthermore, based on these sorption reactions, we demonstrate the ability of an attached S. natans biofilm to remove uranium from solution without any filtration step.

Structure and thermodynamic stability of UTa 3O 10, aU(v)-bearing compound

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

Guo, Xiaofeng; Lipp, Christian; Tiferet, Eitan

Heating a mixture of uranyl (VI) nitrate and tantalum (V) oxide in the molar ratio of 2 : 3 to 1400 °C resulted in the formation of a new compound, UTa 3O 10. The honey colored to yellow brown crystals of UTa 3O 10 crystallize in an orthorhombic structure with the space group Fddd (no. 70), lattice parameters a = 7.3947(1), b = 12.7599(2), c = 15.8156(2) Å, and Z = 8. Vertex sharing [TaO 6] 7– octahedra of two crystallographically distinct Ta cations form a three dimensional tantalate framework. Within this framework, six membered rings of [TaO 6] 7–more » octahedra are formed within the (001) plane. The center of these rings is occupied by the uranyl cations [UO 2]+, with an oxidation state of +5 for uranium. The pentavalence of U and Ta was confirmed by X-ray photoelectron spectroscopy and X-ray adsorption spectroscopy. The enthalpy of formation of UTa 3O 10 from Ta 2O 5, β-U 3O 7, and U3O8 has been determined to be 13.1 ± 18.1 kJ mol–1 using high temperature oxide melt solution calorimetry with sodium molybdate as the solvent at 700 °C. As a result, the close to zero enthalpy of formation of UTa 3O 10 can be explained by closely balanced structural stabilizing and destabilizing factors, which may also apply to other UM 3O 10 compounds.« less

Structure and thermodynamic stability of UTa 3O 10, aU(v)-bearing compound

DOE PAGES

Guo, Xiaofeng; Lipp, Christian; Tiferet, Eitan; ...

2016-09-09

Heating a mixture of uranyl (VI) nitrate and tantalum (V) oxide in the molar ratio of 2 : 3 to 1400 °C resulted in the formation of a new compound, UTa 3O 10. The honey colored to yellow brown crystals of UTa 3O 10 crystallize in an orthorhombic structure with the space group Fddd (no. 70), lattice parameters a = 7.3947(1), b = 12.7599(2), c = 15.8156(2) Å, and Z = 8. Vertex sharing [TaO 6] 7– octahedra of two crystallographically distinct Ta cations form a three dimensional tantalate framework. Within this framework, six membered rings of [TaO 6] 7–more » octahedra are formed within the (001) plane. The center of these rings is occupied by the uranyl cations [UO 2]+, with an oxidation state of +5 for uranium. The pentavalence of U and Ta was confirmed by X-ray photoelectron spectroscopy and X-ray adsorption spectroscopy. The enthalpy of formation of UTa 3O 10 from Ta 2O 5, β-U 3O 7, and U3O8 has been determined to be 13.1 ± 18.1 kJ mol–1 using high temperature oxide melt solution calorimetry with sodium molybdate as the solvent at 700 °C. As a result, the close to zero enthalpy of formation of UTa 3O 10 can be explained by closely balanced structural stabilizing and destabilizing factors, which may also apply to other UM 3O 10 compounds.« less

The mechanism of CO2 hydration: a porous metal oxide nanocapsule catalyst can mimic the biological carbonic anhydrase role.

PubMed

Bandeira, Nuno A G; Garai, Somenath; Müller, Achim; Bo, Carles

2015-11-04

The mechanism for the hydration of CO2 within a Keplerate nanocapsule is presented. A network of hydrogen bonds across the water layers in the first metal coordination sphere facilitates the proton abstraction and nucleophilic addition of water. The highly acidic properties of the polyoxometalate cluster are crucial for explaining the catalysed hydration.

The effect of Si and Al concentrations on the removal of U(VI) in the alkaline conditions created by NH3 gas

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

Katsenovich, Yelena P.; Cardona, Claudia; Lapierre, Robert

2016-10-01

Remediation of uranium in the deep unsaturated zone is a challenging task, especially in the presence of oxygenated, high-carbonate alkalinity soil and pore water composition typical for arid and semi-arid environments of the western regions of the U.S. This study evaluates the effect of various pore water constituencies on changes of uranium concentrations in alkaline conditions, created in the presence of reactive gases such as NH3 to effectively mitigate uranium contamination in the vadose zone sediments. This contaminant is a potential source for groundwater pollution through slow infiltration of soluble and highly mobile uranium species towards the water table. Themore » objective of this research was to evaluate uranium sequestration efficiencies in the alkaline synthetic pore water solutions prepared in a broad range of Si, Al, and bicarbonate concentrations typically present in field systems of the western U.S. regions and identify solid uranium-bearing phases that result from ammonia gas treatment. In previous studies (Szecsody et al. 2012; Zhong et al. 2015), although uranium mobility was greatly decreased, solid phases could not be identified at the low uranium concentrations in field-contaminated sediments. The chemical composition of the synthetic pore water used in the experiments varied for silica (5–250 mM), Al3+ (2.8 or 5 mM), HCO3- (0–100 mM) and U(VI) (0.0021–0.0084 mM) in the solution mixture. Experiment results suggested that solutions with Si concentrations higher than 50 mM exhibited greater removal efficiencies of U(VI). Solutions with higher concentrations of bicarbonate also exhibited greater removal efficiencies for Si, Al, and U(VI). Overall, the silica polymerization reaction leading to the formation of Si gel correlated with the removal of U(VI), Si, and Al from the solution. If no Si polymerization was observed, there was no U removal from the supernatant solution. Speciation modeling indicated that the dominant uranium species in the presence of bicarbonate were anionic uranyl carbonate complexes (UO2(CO3)2-2 and UO2(CO3)3-4) and in the absence of bicarbonate in the solution, U(VI) major species appeared as uranyl-hydroxide (UO2(OH)3- and UO2(OH)4-2) species. The model also predicted the formation of uranium solid phases. Uranyl carbonates as rutherfordine [UO2CO3], cejkaite [Na4(UO2)(CO3)3] and hydrated uranyl silicate phases as Na-boltwoodite [Na(UO2)(SiO4)·1.5H2O] were anticipated for most of the synthetic pore water compositions amended from medium (2.9 mM) to high (100 mM) bicarbonate concentrations.« less

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.

Leaching under Oxygen Pressure with Carbonate Solution Reduction by Hydrogen; LIXIVIATION OXYDANTE DES PECHBLENDES ET PRECIPITATION DE L'URANIUM PAR L'HYDROGENE. APPLICATION AUX MINERAIS PAUVRES FRANCAIS

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

Balaceanu, J.C.; Coussemant, F.; Mouret, P.

1959-10-31

A study was made of the basic characteristics of the leaching with carbonate solution under oxygen pressure and of the catalytic hydrogen reduction of low-grade French ores. Pure U/sub 3/O/sub 8/ was used in the investigations on leaching. The effects of oxygen pressure, temperature, initial surface of the oxide, surfuce during the course of the reaction, and concentration of the carbonate solution were determined. It was shown that the heterogeneous reactions involve a constant surface and two steps. A pilot plant experiment was made on a number of low-grade French ores. With ores the leaching is not sensitive to oxygenmore » pressure. Dilute solutions of sodium uranyl carbonate are obtained from the leaching. The uranium can be precipitated as an oxide of a lower valent state by catalytic reduction with hydrogen. The study of this step was made on pure solutions of sodium uranyl carbonate in the presence of nickel and platinum catalysts. The reaction is strongly modified by the presence of even low concentrations of sodium bicarbonate. The reaction velocity increases with hydrogen pressure up to 5 atm, but then becomes independent of the pressure. The precipitation is accelerated by an increase in temperature. (J.S.R.)« 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.

Kinetic effects of sulfur oxidation on catalytic nitrile hydration: nitrile hydratase insights from bioinspired ruthenium(II) complexes.

PubMed

Kumar, Davinder; Nguyen, Tho N; Grapperhaus, Craig A

2014-12-01

Kinetic investigations inspired by the metalloenzyme nitrile hydratase were performed on a series of ruthenium(II) complexes to determine the effect of sulfur oxidation on catalytic nitrile hydration. The rate of benzonitrile hydration was quantified as a function of catalyst, nitrile, and water concentrations. Precatalysts L(n)RuPPh3 (n = 1-3; L(1) = 4,7-bis(2'-methyl-2'-mercapto-propyl)-1-thia-4,7-diazacyclononane; L(2) = 4-(2'-methyl-2'-sulfinatopropyl)-7-(2'-methyl-2'-mercapto-propyl)-1-thia-4,7-diazacyclononane; L(3) = 4-(2'-methyl-2'-sulfinatopropyl)-7-(2'-methyl-2'-sulfenato-propyl)-1-thia-4,7-diazacyclononane) were activated by substitution of triphenylphosphine with substrate in hot dimethylformamide solution. Rate measurements are consistent with a dynamic equilibrium between inactive aqua (L(n)Ru-OH2) and active nitrile (L(n)Ru-NCR) derivatives with K = 21 ± 1, 9 ± 0.9, and 23 ± 3 for L(1) to L(3), respectively. Subsequent hydration of the L(n)Ru-NCR intermediate yields the amide product with measured hydration rate constants (k's) of 0.37 ± 0.01, 0.82 ± 0.07, and 1.59 ± 0.12 M(-1) h(-1) for L(1) to L(3), respectively. Temperature dependent studies reveal that sulfur oxidation lowers the enthalpic barrier by 27 kJ/mol, but increases the entropic barrier by 65 J/(mol K). Density functional theory (DFT) calculations (B3LYP/LanL2DZ (Ru); 6-31G(d) (all other atoms)) support a nitrile bound catalytic cycle with lowering of the reaction barrier as a consequence of sulfur oxidation through enhanced nitrile binding and attack of the water nucleophile through a highly organized transition state.

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.

Mineralogical Study of Hydrated IDPs: X-Ray Diffraction and Transmission Electron Microscopy

NASA Technical Reports Server (NTRS)

Nakamura, K.; Keller, L. P.; Nakamura, T.; Noguchi, T.; Zolensky, M. E.

2004-01-01

Chondritic hydrated interplanetary dust particles (IDPs) comprise up to 50% of all IDPs collected in the stratosphere [1]. Hydrated IDPs are generally believed to be derived from asteroidal sources that have undergone aqueous alteration. However, the high C contents of hydrated IDPs (by 2 to 6X CI levels [2,3]) indicate that they are probably not derived from the same parent bodies sampled by the known chondritic meteorites. Some hydrated IDPs exhibit large deuterium enrichments [4] similar to those observed in anhydrous IDPs. Both anhydrous and hydrated IDPs contain a variety of anhydrous minerals such as silicates, sulfides, oxides, and carbonates. Controversies on hydrated IDPs still exist regarding their formation, history, and relationship to other primitive solar system materials, because of the lack of a systematic series of analysis on individual hydrated IDPs. In this study, we combine our observations of the bulk mineralogy, mineral/ organic chemistry in order to derive a more complete picture of hydrated IDPs.

Hydration of dimethyldodecylamine-N-oxide: enthalpy and entropy driven processes.

PubMed

Kocherbitov, Vitaly; Söderman, Olle

2006-07-13

Dimethyldodecylamine-N-oxide (DDAO) has only one polar atom that is able to interact with water. Still, this surfactant shows very hydrophilic properties: in mixtures with water, it forms normal liquid crystalline phases and micelles. Moreover, there is data in the literature indicating that the hydration of this surfactant is driven by enthalpy while other studies show that hydration of surfactants and lipids typically is driven by entropy. Sorption calorimetry allows resolving enthalpic and entropic contributions to the free energy of hydration at constant temperature and thus directly determines the driving forces of hydration. The results of the present sorption calorimetric study show that the hydration of liquid crystalline phases of DDAO is driven by entropy, except for the hydration of the liquid crystalline lamellar phase which is co-driven by enthalpy. The exothermic heat effect of the hydration of the lamellar phase arises from formation of strong hydrogen bonds between DDAO and water. Another issue is the driving forces of the phase transitions caused by the hydration. The sorption calorimetric results show that the transitions from the lamellar to cubic and from the cubic to the hexagonal phase are driven by enthalpy. Transitions from solid phases to the liquid crystalline lamellar phase are entropically driven, while the formation of the monohydrate from the dry surfactant is driven by enthalpy. The driving forces of the transition from the hexagonal phase to the isotropic solution are close to zero. These sorption calorimetric results are in good agreement with the analysis of the binary phase diagram based on the van der Waals differential equation. The phase diagram of the DDAO-water system determined using DSC and sorption calorimetry is presented.

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

High capacity nickel battery material doped with alkali metal cations

DOEpatents

Jackovitz, John F.; Pantier, Earl A.

1982-05-18

A high capacity battery material is made, consisting essentially of hydrated Ni(II) hydroxide, and about 5 wt. % to about 40 wt. % of Ni(IV) hydrated oxide interlayer doped with alkali metal cations selected from potassium, sodium and lithium cations.

Alkali slurry ozonation to produce a high capacity nickel battery material

DOEpatents

Jackovitz, John F.; Pantier, Earl A.

1984-11-06

A high capacity battery material is made, consisting essentially of hydrated Ni(II) hydroxide, and about 5 wt. % to about 40 wt. % of Ni(IV) hydrated oxide interlayer doped with alkali metal cations selected from potassium, sodium and lithium cations.

The Extent of CH4 Emission and Oxidation in Thermogenic and Biogenic Gas Hydrate Environments

NASA Astrophysics Data System (ADS)

Kastner, M.; Solem, C.; Bartlett, D.; MacDonald, I.; Valentine, D.

2003-12-01

The role of methane hydrate in the global methane budget is poorly understood, because relatively little is known about the transport of gaseous and dissolved methane through the seafloor into the ocean, from the water column into the atmosphere, and the extent of water-column methanotrophy that occurs en route. We characterize the transport and consumption of methane in three distinct gas hydrate environments, spanning the spectrum of thermogenic and biogenic methane occurrences: Bush Hill in the Gulf of Mexico, Eel River off the coast of Northern California, and the Noth and South Hydrate Ridges on the Cascadia Oregon margin. At all the sites studied a significant enrichment in δ 13CH4 with distance along isopycnals away from the methane source is observed, indicative of extensive aerobic bacterial methane oxidation in the water column. The effects of this process are principally pronounced in the mostly biogenic methane setting, with δ 13C-CH4 measured as high as -12 permil (PDB) between North and South Hydrate Ridge. The δ 13C-CH4 values ranged from -12 to -67 permil at Hydrate Ridge, -34 to -52 permil at Eel River, and -41 to -49 permil at Bush Hill. The large variation in methane carbon isotope ranges between the sites suggest that major differences exist in both the rates of aerobic methane oxidation and system openness at the studied locations. A mean kinetic isotope fractionation factor is being determined using a closed-system Rayleigh distillation model. An approximate regional methane flux from the ocean into the atmosphere is being estimated for the Gulf of Mexico, by extrapolation of the flux value from the Bush Hill methane plume over 390 plume locations having persistent oil slicks on the ocean surface, mapped by time series satellite data.

75 FR 36701 - Issuance of Environmental Assessment and Finding of No Significant Impact for Modification of...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-06-28

... in the form of highly water soluble uranyl fluoride. EnergySolutions also proposed the addition of...; the concentration of residual uranyl fluoride in the K-25 piping waste in the railcars would likely... soluble uranyl fluoride in quantities in excess of the limits in Condition 4 of the 2006 Order (i.e., up...

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.

Development of a Scalable Process Control System for Chemical Soil Washing to Remove Uranyl Oxide

DTIC Science & Technology

2015-05-01

ICET also has a fully equipped counting laboratory for the evaluation of radioactive samples . Photographs of the 1-meter and 3-meter motorized...the leachate will be monitored using a gamma detector. There are numerous naturally occurring radioactive materials in soil . ICET has developed a...48.6% from 238U and 49.2% from 234U. The 238U in NU also contains daughters that are radioactive . This increases the activity of samples over long

40 CFR 98.190 - Definition of the source category.

Code of Federal Regulations, 2010 CFR

2010-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Lime Manufacturing § 98.190 Definition of the source category. (a) Lime manufacturing plants (LMPs) engage in the manufacture of a lime product (e.g., calcium oxide, high-calcium quicklime, calcium hydroxide, hydrated lime, dolomitic quicklime, dolomitic hydrate, or...

Novel hydrated graphene ribbon unexpectedly promotes aged seed germination and root differentiation

NASA Astrophysics Data System (ADS)

Hu, Xiangang; Zhou, Qixing

2014-01-01

It is well known that graphene (G) induces nanotoxicity towards living organisms. Here, a novel and biocompatible hydrated graphene ribbon (HGR) unexpectedly promoted aged (two years) seed germination. HGR formed at the normal temperature and pressure (120 days hydration), presented 17.1% oxygen, 0.9% nitrogen groups, disorder-layer structure, with 0.38 nm thickness ribbon morphology. Interestingly, there were bulges around the edges of HGR. Compared to G and graphene oxide (GO), HGR increased seed germination by 15% root differentiation between 52 and 59% and enhanced resistance to oxidative stress. The metabonomics analysis discovered that HGR upregulated carbohydrate, amino acid, and fatty acids metabolism that determined secondary metabolism, nitrogen sequestration, cell membrane integrity, permeability, and oxidation resistance. Hexadecanoic acid as a biomarker promoted root differentiation and increased the germination rate. Our discovery is a novel HGR that promotes aged seed germination, illustrates metabolic specificity among graphene-based materials, and inspires innovative concepts in the regulation of seed development.

Electrochemical oxidation of hydrazine and its derivatives on the surface of metal electrodes in alkaline media

NASA Astrophysics Data System (ADS)

Asazawa, Koichiro; Yamada, Koji; Tanaka, Hirohisa; Taniguchi, Masatoshi; Oguro, Keisuke

Electrochemical oxidation of hydrazine and its derivatives on the surface of various metal electrodes in alkaline media was investigated. A comparison of various polycrystalline metal electrodes (Ni, Co, Fe, Cu, Ag, Au, and Pt) showed that Co and Ni electrodes have a lower onset potential for hydrazine oxidation than the Pt electrode. The onset oxidation potential of APA (aminopolyacrylamide), a hydrazine derivative (-0.127 V vs. reversible hydrogen electrode, RHE), was similar to that of hydrazine hydrate (-0.178 V vs. RHE) in the case of the Co electrode. APA oxidation was possible because of hydrazine desorption that was caused by APA hydrolysis. The hydrolysis reaction was brought about by a heat treatment. This result suggests that the hydrazine hydrolysis reaction of hydrazine derivatives makes it possible to store hydrazine hydrate safely.

Facile Reductive Silylation of UO22+ to Uranium(IV) Chloride.

PubMed

Kiernicki, John J; Zeller, Matthias; Bart, Suzanne C

2017-01-19

General reductive silylation of the UO 2 2+ cation occurs readily in a one-pot, two-step stoichiometric reaction at room temperature to form uranium(IV) siloxides. Addition of two equivalents of an alkylating reagent to UO 2 X 2 (L) 2 (X=Cl, Br, I, OTf; L=triphenylphosphine oxide, 2,2'-bipyridyl) followed by two equivalents of a silyl (pseudo)halide, R 3 Si-X (R=aryl, alkyl, H; X=Cl, Br, I, OTf, SPh), cleanly affords (R 3 SiO) 2 UX 2 (L) 2 in high yields. Support is included for the key step in the process, reduction of U VI to U V . This procedure is applicable to a wide range of commercially available uranyl salts, silyl halides, and alkylating reagents. Under this protocol, one equivalent of SiCl 4 or two equivalents of Me 2 SiCl 2 results in direct conversion of the uranyl to uranium(IV) tetrachloride. Full spectroscopic and structural characterization of the siloxide products is reported. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular dynamics simulations reveal that water diffusion between graphene oxide layers is slow

DOE PAGES

Devanathan, Ram; Chase-Woods, Dylan; Shin, Yongsoon; ...

2016-07-08

Membranes made of stacked layers of graphene oxide (GO) hold the tantalizing promise of revolutionizing desalination and water filtration if selective transport of molecules can be controlled. We present the findings of a molecular dynamics simulation study of water intercalated between GO layers that have a C/O ratio of 4. We simulated a range of hydration levels from 1 wt.% to 23.3 wt.% water. The interlayer spacing increased upon hydration from 0.8 nm to 1.1 nm. We also synthesized GO membranes that showed an increase in spacing from about 0.7 nm to 0.8 nm and an increase in mass ofmore » about 14% on hydration. Water diffusion through GO layers is an order of magnitude slower than that in bulk water, because of strong hydrogen bonded interactions. Most of the water molecules are bound to OH groups even at the highest hydration level. We observed large water clusters that could span graphitic regions, oxidized regions and holes that have been experimentally observed in GO. As a result, slow interlayer diffusion can be consistent with experimentally observed water transport in GO if holes lead to a shorter path length than previously assumed and sorption serves as a key rate-limiting step.« less

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.

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.

Poly(2,6-dimethyl-1,4-phenylene oxide) Blended with Poly (vinylbenzyl chloride)-b-polystyrene for the Formation of Anion Exchange Membranes

DTIC Science & Technology

2014-08-14

show improved mechanical properties compared to the styrenic copolymer, particularly in a hydrated condition. The membranes were subjected to...AEMs) show improved mechanical properties compared to the styrenic copolymer, particularly in a hydrated condition. The membranes were subjected to...deionized water, and after 24 h of soaking, the fully hydrated membranes were removed from the water; any residual bulk water on the membrane surface was

E-beam and UV induced fabrication of CeO2, Eu2O3 and their mixed oxides with UO2

NASA Astrophysics Data System (ADS)

Pavelková, Tereza; Vaněček, Vojtěch; Jakubec, Ivo; Čuba, Václav

2016-07-01

CeO2, Eu2O3 and mixed oxides of CeO2-UO2, Eu2O3-UO2 were fabricated. The preparative method was based on the irradiation of aqueous solutions containing cerium/europium (and uranyl) nitrates and ammonium formate. In the course of irradiation, the solid phase (precursor) was precipitated. The composition of irradiated solutions significantly affected the properties of precursor formed in the course of the irradiation. However, subsequent heat treatment of (amorphous) precursors at temperatures ≤650 °C invariably resulted in the formation of powder oxides with well-developed nanocrystals with linear crystallite size 13-27 nm and specific surface area 10-46 m2 g-1. The applicability of both ionizing (e-beam) and non-ionizing (UV) radiation was studied.

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.

Ruthenium on chitosan: A recyclable heterogeneous catalyst for aqueous hydration of nitriles to amides

EPA Science Inventory

Ruthenium has been immobilized over chitosan by simply stirring an aqueous suspension of chitosan in water with ruthenium chloride and has been utilized for the oxidation of nitriles to amides; the hydration of nitriles occurs in high yield and excellent selectivity, which procee...

PRECIPITATION CHEMISTRY OF MAGNESIUM SULFITE HYDRATES IN MAGNESIUM OXIDE SCRUBBING

EPA Science Inventory

The report gives results of laboratory studies defining the precipitation chemistry of MgSO3 hydrates. The results apply to the design of Mg-based scrubbing processes for SO2 removal from combustion flue gas. In Mg-based scrubbing processes, MgSO3 precipitates as either trihydrat...

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

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.

The interplay of protein and solvent picosecond dynamics: Experimental and theoretical studies

NASA Astrophysics Data System (ADS)

He, Yunfen

Terahertz gap is located between microwaves and infrared. THz-TDS is based on the generation of subpicosecond terahertz pulses using ultrashort laser pulses with pulse durations of a few femtoseconds. From the spectroscopic point of view terahertz radiation excites the low frequency vibrations of molecules. Terahertz spectroscopy provides a new way to study protein dynamics in this critical frequency range. The strong temperature dependence of molecular flexibility near 200 K for proteins and polynucleotides hydrated above 30% by weight, dynamical transition, is one of the most significant phenomena of biomolecular dynamics. Measurements of the dynamical transition were performed for native, fully denatured and unstructured polypeptides using THz-TDS. The results reveal that the dynamical transition is independent of either tertiary or secondary structure. The transition are also found for shorter chain alanine peptides down to penta-alanine, which indicates that a quantitative predictive theory for the temperature dependence lies in the understanding of the interaction of the side chains of the poly peptide or poly nucleotide with the biological water. The far infrared vibrational modes can be calculated using harmonic or anharmonic normal mode analysis, and the resulting Density of States (DOS) strongly resembles the measured absorbance. A large contrast in the terahertz dielectric response between oxidized and reduced cytochrome c has lready been observed experimentally. This large contrast has been associated with a change in the collective structural motions that related to protein flexibility. Molecular simulation results from quasiharmonic analysis and dipole-dipole correlation analysis are compared with the measurements to determine the relative contribution of correlated motions and diffusive motions to the measured dielectric response. The measured hydration dependence is reproduced by hydration dependence of quasiharmonic normal modes, but these modes calculations do not reproduce the oxidation dependence. Whereas dipole-dipole correlation analysis reproduces the oxidation dependence at the lowest hydration level, but surprisingly do not capture the hydration dependence. These results suggest that the hydration dependence in the THz response does in fact arise from changes in the vibrational modes, and the oxidation dependence arises from relaxational motions.

Surface reactions kinetics between nanocrystalline magnetite and uranyl.

PubMed

Missana, Tiziana; Maffiotte, César; García-Gutiérrez, Miguel

2003-05-01

Magnetite is the most important end member of iron corrosion products under reducing environment, which is the condition expected in a deep geological high level radioactive waste disposal. Nanocrystalline magnetite was synthesized in the laboratory and its physicochemical properties were analyzed in detail. The kinetics of the adsorption of U(VI) and the kinetics of the actinide reduction to a lower oxidation state, in presence of the oxide, were studied by means of batch sorption techniques and X-ray photoelectron spectroscopy (XPS) analysis. The results showed that the uranium sorption and reduction processes on the magnetite surface have very fast kinetics (hours), the reduction process being triggered by sorption. XPS measurements showed that the speciation of uranium at the surface does not show significant changes with time (from 1 day to 3 months), as well as the quantity of uranium detected at the surface. The surface speciation depended on the initial pH of the contact solution. Considering that the Eh of equilibrium between magnetite and the solution, under our experimental conditions, is slightly positive (50-100 mV), the uranium reduction would also be thermodynamically possible within the liquid phase. However, the kinetics of reduction in the liquid occur at a much slower rate which, in turn, has to depend on the attainment of the magnetite/solution equilibrium. The decrease of uranium in solution, observed after the uranyl adsorption stage, and particularly at acidic pH, is most probably due to the precipitation of U(IV) formed in the solution.

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.

Paving asphalts : reduction of oxidative hardening of asphalts by treatment with hydrated lime : a mechanistic study

DOT National Transportation Integrated Search

1977-04-01

This study showed that lime treatment removes polar, viscosity-building components and reduces the susceptibility of the asphalt to laboratory oxidative hardening. The beneficial effects of lime treatment in reducing asphalt oxidative hardening were ...

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

Water flow in carbon-based nanoporous membranes impacted by interactions between hydrated ions and aromatic rings.

PubMed

Liu, Jian; Shi, Guosheng; Fang, Haiping

2017-02-24

Carbon-based nanoporous membranes, such as carbon nanotubes (CNTs), graphene/graphene oxide and graphyne, have shown great potential in water desalination and purification, gas and ion separation, biosensors, and lithium-based batteries, etc. A deep understanding of the interaction between hydrated ions in an aqueous solution and the graphitic surface in systems composed of water, ions and a graphitic surface is essential for applications with carbon-based nanoporous membrane platforms. In this review, we describe the recent progress of the interaction between hydrated ions and aromatic ring structures on the carbon-based surface and its applications in the water flow in a carbon nanotube. We expect that these works can be extended to the understanding of water flow in other nanoporous membranes, such as nanoporous graphene, graphyne and stacked sheets of graphene oxide.

SEPARATION OF RUTHENIUM FROM AQUEOUS SOLUTIONS

DOEpatents

Callis, C.F.; Moore, R.L.

1959-09-01

>The separation of ruthenium from aqueous solutions containing uranium plutonium, ruthenium, and fission products is described. The separation is accomplished by providing a nitric acid solution of plutonium, uranium, ruthenium, and fission products, oxidizing plutonium to the hexavalent state with sodium dichromate, contacting the solution with a water-immiscible organic solvent, such as hexone, to extract plutonyl, uranyl, ruthenium, and fission products, reducing with sodium ferrite the plutonyl in the solvent phase to trivalent plutonium, reextracting from the solvent phase the trivalent plutonium, ruthenium, and some fission products with an aqueous solution containing a salting out agent, introducing ozone into the aqueous acid solution to oxidize plutonium to the hexavalent state and ruthenium to ruthenium tetraoxide, and volatizing off the ruthenium tetraoxide.

Evidence of Methane Outgassing During MIS3 in the Bering Sea

NASA Astrophysics Data System (ADS)

Cook, M. S.; Keigwin, L. D.

2005-12-01

There are multiple negative excursions in planktonic and benthic foraminifer δ13C in a core from 1467m in the southeast Bering Sea. These excursions occur episodically during the last glacial period, and may coincide with Dansgaard-Oeschger (D-O) events. Measured foraminifer δ13C during the excursions is as low as -14‰ and are probably the result of overgrowths of diagenetic calcium carbonate. We estimate overgrowth δ13C is -23‰, and hypothesize that the occurrence of overgrowths is associated with anaerobic oxidation of biogenic methane. The likely pressure and temperature conditions at this site and during the last glacial period were well within the zone of methane-hydrate stability, so the source of methane is probably not from destabilization of methane hydrate at this depth. The methane may have originated from increased in-situ methanogenesis resulting from greater burial of organic carbon, or from destabilization of methane hydrate at shallower sites near the methane-hydrate stability threshold. Both these scenarios could be active, consistent with the ``Clathrate Gun Hypothesis'' (Kennett et al., 2003), in which there is widespread destabilization of marine methane hydrates during D-O events, where methane gas both is oxidized within the water column and escapes to the atmosphere.

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

4. VIEW OF ROOM 103 IN 1980. SIX OF THE ...

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

4. VIEW OF ROOM 103 IN 1980. SIX OF THE NINE URANIUM NITRATE STORAGE TANKS ARE SHOWN. HIGHLY ENRICHED URANIUM WAS INTRODUCED INTO THE BUILDING IN THE SUMMER OF 1965 AND THE FIRST EXPERIMENTS WERE PERFORMED IN SEPTEMBER OF 1965. EXPERIMENTS WERE PERFORMED ON ENRICHED URANIUM METAL AND SOLUTION, PLUTONIUM METAL, LOW ENRICHED URANIUM OXIDE, AND SEVERAL SPECIAL APPLICATIONS. AFTER 1983, EXPERIMENTS WERE CONDUCTED PRIMARILY WITH URANYL NITRATE SOLUTIONS, AND DID NOT INVOLVE SOLID MATERIALS. - Rocky Flats Plant, Critical Mass Laboratory, Intersection of Central Avenue & 86 Drive, Golden, Jefferson County, CO

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.

PREPARATION OF URANIUM TRIOXIDE

DOEpatents

Buckingham, J.S.

1959-09-01

The production of uranium trioxide from aqueous solutions of uranyl nitrate is discussed. The uranium trioxide is produced by adding sulfur or a sulfur-containing compound, such as thiourea, sulfamic acid, sulfuric acid, and ammonium sulfate, to the uranyl solution in an amount of about 0.5% by weight of the uranyl nitrate hexahydrate, evaporating the solution to dryness, and calcining the dry residue. The trioxide obtained by this method furnished a dioxide with a considerably higher reactivity with hydrogen fluoride than a trioxide prepared without the sulfur additive.

ELECTROLYTIC PRODUCTION OF URANIUM TETRAFLUORIDE

DOEpatents

Lofthouse, E.

1954-08-31

This patent relates to electrolytic methods for the production of uranium tetrafluoride. According to the present invention a process for the production of uranium tetrafluoride comprises submitting to electrolysis an aqueous solution of uranyl fluoride containing free hydrofluoric acid. Advantageously the aqueous solution of uranyl fluoride is obtained by dissolving uranium hexafluoride in water. On electrolysis, the uranyl ions are reduced to uranous tons at the cathode and immediately combine with the fluoride ions in solution to form the insoluble uranium tetrafluoride which is precipitated.

Sorption of uranyl ions from various acido systems by amphoteric epoxy amine ion-exchange resins

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

Rychkov, V.N.; Radionov, B.K.; Molochnikov, L.S.

1995-03-01

Sorption of uranyl ions by epoxy amine ampholytes with N-monomethylenephosphonic acid groups modified with pyridine or quaternary ammonium groups was studied under dynamic conditions. Heterocyclic nitrogen favors sorption of uranyl ion from fluoride, sulfate, and fluoride-sulfate solutions. The ESR studies of mono- and bimetallic forms of nitrogen-containing ampholytes with copper(II) as paramagnetic marker revealed the characteristics of uranium(VI) interaction with cation- and anion-exchange groups and its dependence on the fluoride content in solution.

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

Dehydration of plutonium or neptunium trichloride hydrate

DOEpatents

Foropoulos, Jr., Jerry; Avens, Larry R.; Trujillo, Eddie A.

1992-01-01

A process of preparing anhydrous actinide metal trichlorides of plutonium or neptunium by reacting an aqueous solution of an actinide metal trichloride selected from the group consisting of plutonium trichloride or neptunium trichloride with a reducing agent capable of converting the actinide metal from an oxidation state of +4 to +3 in a resultant solution, evaporating essentially all the solvent from the resultant solution to yield an actinide trichloride hydrate material, dehydrating the actinide trichloride hydrate material by heating the material in admixture with excess thionyl chloride, and recovering anhydrous actinide trichloride is provided.

Dehydration of plutonium or neptunium trichloride hydrate

DOEpatents

Foropoulos, J. Jr.; Avens, L.R.; Trujillo, E.A.

1992-03-24

A process is described for preparing anhydrous actinide metal trichlorides of plutonium or neptunium by reacting an aqueous solution of an actinide metal trichloride selected from the group consisting of plutonium trichloride or neptunium trichloride with a reducing agent capable of converting the actinide metal from an oxidation state of +4 to +3 in a resultant solution, evaporating essentially all the solvent from the resultant solution to yield an actinide trichloride hydrate material, dehydrating the actinide trichloride hydrate material by heating the material in admixture with excess thionyl chloride, and recovering anhydrous actinide trichloride.

Flowsheet Analysis of U-Pu Co-Crystallization Process as a New Reprocessing System

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

Shunji Homma; Jun-ichi Ishii; Jiro Koga

2006-07-01

A new fuel reprocessing system by U-Pu co-crystallization process is proposed and examined by flowsheet analysis. This reprocessing system is based on the fact that hexavalent plutonium in nitric acid solution is co-crystallized with uranyl nitrate, whereas it is not crystallized when uranyl nitrate does not exist in the solution. The system consists of five steps: dissolution of spent fuel, plutonium oxidation, U-Pu co-crystallization as a co-decontamination, re-dissolution of the crystals, and U re-crystallization as a U-Pu separation. The system requires a recycling of the mother liquor from the U-Pu co-crystallization step and the appropriate recycle ratio is determined bymore » flowsheet analysis such that the satisfactory decontamination is achieved. Further flowsheet study using four different compositions of LWR spent fuels demonstrates that the constant ratio of plutonium to uranium in mother liquor from the re-crystallization step is achieved for every composition by controlling the temperature. It is also demonstrated by comparing to the Purex process that the size of the plant based on the proposed system is significantly reduced. (authors)« less

Conceptual designs of NDA instruments for the NRTA system at the Rokkasho Reprocessing Plant

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

Li, T.K.; Klosterbuer, S.F.; Menlove, H.O.

The authors are studying conceptual designs of selected nondestructive assay (NDA) instruments for the near-real-time accounting system at the rokkasho Reprocessing Plant (RRP) of Japan Nuclear Fuel Limited (JNFL). The JNFL RRP is a large-scale commercial reprocessing facility for spent fuel from boiling-water and pressurized-water reactors. The facility comprises two major components: the main process area to separate and produce purified plutonium nitrate and uranyl nitrate from irradiated reactor spent fuels, and the co-denitration process area to combine and convert the plutonium nitrate and uranyl nitrate into mixed oxide (MOX). The selected NDA instruments for conceptual design studies are themore » MOX-product canister counter, holdup measurement systems for calcination and reduction furnaces and for blenders in the co-denitration process, the isotope dilution gamma-ray spectrometer for the spent fuel dissolver solution, and unattended verification systems. For more effective and practical safeguards and material control and accounting at RRP, the authors are also studying the conceptual design for the UO{sub 3} large-barrel counter. This paper discusses the state-of-the-art NDA conceptual design and research and development activities for the above instruments.« 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.

Synthesis and structure characterization of chromium oxide prepared by solid thermal decomposition reaction.

PubMed

Li, Li; Yan, Zi F; Lu, Gao Q; Zhu, Zhong H

2006-01-12

Mesoporous chromium oxide (Cr2O3) nanocrystals were first synthesized by the thermal decomposition reaction of Cr(NO3)3.9H2O using citric acid monohydrate (CA) as the mesoporous template agent. The texture and chemistry of chromium oxide nanocrystals were characterized by N2 adsorption-desorption isotherms, FTIR, X-ray diffraction (XRD), UV-vis, and thermoanalytical methods. It was shown that the hydrate water and CA are the crucial factors in influencing the formation of mesoporous Cr2O3 nanocrystals in the mixture system. The decomposition of CA results in the formation of a mesoporous structure with wormlike pores. The hydrate water of the mixture provides surface hydroxyls that act as binders, making the nanocrystals aggregate. The pore structures and phases of chromium oxide are affected by the ratio of precursor-to-CA, thermal temperature, and time.

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.

Methanogenic calcite, 13C-depleted bivalve shells, and gas hydrate from a mud volcano offshore southern California

USGS Publications Warehouse

Hein, J.R.; Normark, W.R.; McIntyre, B.R.; Lorenson, T.D.; Powell, C.L.

2006-01-01

Methane and hydrogen sulfide vent from a cold seep above a shallowly buried methane hydrate in a mud volcano located 24 km offshore southern California in?? 800 m of water. Bivalves, authigenic calcite, and methane hydrate were recovered in a 2.1 m piston core. Aragonite shells of two bivalve species are unusually depleted in 13C (to -91??? ??13C), the most 13C-depleted shells of marine macrofauna yet discovered. Carbon isotopes for both living and dead specimens indicate that they used, in part, carbon derived from anaerobically oxidized methane to construct their shells. The ??13C values are highly variable, but most are within the range -12??? to -91???. This variability may be diagnostic for identifying cold-seep-hydrate systems in the geologic record. Authigenic calcite is abundant in the cores down to ???1.5 m subbottom, the top of the methane hydrate. The calcite is depleted in 13C (??13C = -46??? to -58???), indicating that carbon produced by anaerobically oxidized methane is the main source of the calcite. Methane sources include a geologic hydrocarbon reservoir from Miocene source rocks, and biogenic and thermogenic degradation of organic matter in basin sediments. Oxygen isotopes indicate that most calcite formed out of isotopic equilibrium with ambient bottom water, under the influence of gas hydrate dissociation and strong methane flux. High metal content in the mud volcano sediment indicates leaching of basement rocks by fluid circulating along an underlying fault, which also allows for a high flux of fossil methane. ?? 2006 Geological Society of America.

Utilization of red mud and Pb/Zn smelter waste for the synthesis of a red mud-based cementitious material.

PubMed

Li, Yuan-Cheng; Min, Xiao-Bo; Ke, Yong; Chai, Li-Yuan; Shi, Mei-Qing; Tang, Chong-Jian; Wang, Qing-Wei; Liang, Yan-Jie; Lei, Jie; Liu, De-Gang

2018-02-15

A new method in which Pb/Zn smelter waste containing arsenic and heavy metals (arsenic sludge), red mud and lime are utilized to prepare red mud-based cementitious material (RCM) is proposed in this study. XRD, SEM, FTIR and unconfined compressive strength (UCS) tests were employed to assess the physicochemical properties of RCM. In addition, ettringite and iron oxide-containing ettringite were used to study the hydration mechanism of RCM. The results show that the UCS of the RCM (red mud+arsenic sludge+lime) was higher than that of the binder (red mud+arsenic sludge). When the mass ratio of m (binder): m (lime) was 94:6 and then maintained 28days at ambient temperature, the UCS reached 12.05MPa. The red mud has potential cementitious characteristics, and the major source of those characteristics was the aluminium oxide. In the red mud-arsenic sludge-lime system, aluminium oxide was effectively activated by lime and gypsum to form complex hydration products. Some of the aluminium in ettringite was replaced by iron to form calcium sulfoferrite hydrate. The BCR and leaching toxicity results show that the leaching concentration was strongly dependent on the chemical speciation of arsenic and the hydration products. Therefore, the investigated red mud and arsenic sludge can be successfully utilized in cement composites to create a red mud-based cementitious material. Copyright © 2017 Elsevier B.V. All rights reserved.

Hydration of cations: a key to understanding of specific cation effects on aggregation behaviors of PEO-PPO-PEO triblock copolymers.

PubMed

Lutter, Jacob C; Wu, Tsung-yu; Zhang, Yanjie

2013-09-05

This work reports results from the interactions of a series of monovalent and divalent cations with a triblock copolymer, poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO). Phase transition temperatures of the polymer in the presence of chloride salts with six monovalent and eight divalent cations were measured using an automated melting point apparatus. The polymer undergoes a two-step phase transition, consisting of micellization of the polymer followed by aggregation of the micelles, in the presence of all the salts studied herein. The results suggest that hydration of cations plays a key role in determining the interactions between the cations and the polymer. The modulation of the phase transition temperature of the polymer by cations can be explained as a balance between three interactions: direct binding of cations to the oxygen in the polymer chains, cations sharing one water molecule with the polymer in their hydration layer, and cations interacting with the polymer via two water molecules. Monovalent cations Na(+), K(+), Rb(+), and Cs(+) do not bind to the polymer, while Li(+) and NH4(+) and all the divalent cations investigated including Mg(2+), Ca(2+), Sr(2+), Ba(2+), Co(2+), Ni(2+), Cu(2+), and Cd(2+) bind to the polymer. The effects of the cations correlate well with their hydration thermodynamic properties. Mechanisms for cation-polymer interactions are discussed.

Properties of Cement Mortar and Ultra-High Strength Concrete Incorporating Graphene Oxide Nanosheets.

PubMed

Lu, Liulei; Ouyang, Dong

2017-07-20

In this work, the effect of graphene oxide nanosheet (GONS) additives on the properties of cement mortar and ultra-high strength concrete (UHSC) is reported. The resulting GONS-cement composites were easy to prepare and exhibited excellent mechanical properties. However, their fluidity decreased with increasing GONS content. The UHSC specimens were prepared with various amounts of GONSs (0-0.03% by weight of cement). Results indicated that using 0.01% by weight of cement GONSs caused a 7.82% in compressive strength after 28 days of curing. Moreover, adding GONSs improved the flexural strength and deformation ability, with the increase in flexural strength more than that of compressive strength. Furthermore, field-emission scanning electron microscopy (FE-SEM) was used to observe the morphology of the hardened cement paste and UHSC samples. FE-SEM observations showed that the GONSs were well dispersed in the matrix and the bonding of the GONSs and the surrounding cement matrix was strong. Furthermore, FE-SEM observation indicated that the GONSs probably affected the shape of the cement hydration products. However, the growth space for hydrates also had an important effect on the morphology of hydrates. The true hydration mechanism of cement composites with GONSs needs further study.

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

Exploring the synthesis and characterization of nanoenergetic materials from sol-gel chemistry

NASA Astrophysics Data System (ADS)

Walker, Jeremy D.

Nanoenergetic composite materials have been synthesized by a sol-gel chemical process where the addition of a weak base molecule induces the gelation of a hydrated metal salt solution. A proposed 'proton scavenging' mechanism, where a weak base molecule extracts a proton from the coordination sphere of the hydrated iron (III) complex in the gelation process to form iron (III) oxide/hydroxide, FeIIIxOyHz, has been confirmed for the weak base propylene oxide (PO), a 1,2 epoxide, as well as for the weak bases tetrahydrofuran (THF), a 1,4 epoxide, and pyridine, a heterocyclic nitrogen-containing compound. Gelation mechanisms for the formation of FeIIIxOyHz from THF and pyridine have been presented and confirmed through pH, XPS, and IR studies. THF follows a similar mechanism as PO, where the epoxide extracts a proton from the coordination sphere of the hydrated iron complex forming a protonated epoxide, which then undergoes irreversible ring-opening after reaction with a nucleophile in solution. Pyridine also extracts a proton from the hydrated metal complex, however, the stable six-membered molecule has low associated ring strain and does not endure ring-opening. Energetic properties for the Fe2O3/Al and RuO 2/Al sol-gel synthesized systems are also presented. Sol-gel chemistry synthesizes x-ray amorphous oxide matrices which contain substantial quantities of residual water and organic species. The iron (III) matrix, formed from the addition of a weak base epoxide molecule to a hydrated iron (III) nitrate solution, consists of stoichiometric Fe2O3, FeO(OH), and Fe(OH)3 and can only definitely be described as of Fe IIIxOyHz. XPS characterization of the metal oxide matrix synthesized from the addition of the weak base propylene oxide to a hydrated ruthenium (III) chloride solution corresponds to that of hydrous ruthenium (IV) oxide. Fe2O3/Al energetic systems were synthesized from the epoxides PO, trimethylene oxide (TMO) and 3,3 dimethyl oxetane (DMO). Energetic systems formed from each epoxide were each synthesized with different components, including: varying concentrations of nano-scale Al, micron Al, and carbon nanotubes. Surface area analysis of the synthesized matrices shows a direct correlation between the surface area of the iron (III) oxide matrix and the quantified exothermic heat of reaction of the energetic material due to the magnitude of the interfacial surface area contact between the iron (III) oxide matrix and the aluminum particles. The Fe2O3(PO)/Al systems possess the highest heat of reaction values due to the oxide surface area available for contact with the aluminum particles. Also, within systems, 1:1 Fe:nano Al samples possess the highest heat of reaction. Samples with nano-scale Al particles start reaction at 430°C, before the melting point of Al, whereas samples containing micron-Al do not react until ˜800°C, after the melting point of Al. The RuO2/Al energetic systems behave differently dependent on the atmosphere the sample is heated. Heating the RuO2/Al samples in an inert atmosphere results in the complete reduction of the ruthenium oxide matrix to Ru(0) before reaction with the aluminum particles. This results in the exothermic formation of RuxAly intermetallics, with the stoichiometry dependent on the initial Ru:Al concentration. However, heating the samples in an oxygen-rich atmosphere results in an exothermic reaction between RuO2 and Al. Post-reaction analysis of these samples reveals the sole existence of ruthenium (IV) oxide as the exothermic reaction vaporizes the aluminum particles.

Is the U-B color sufficient for identifying water of hydration on solar system bodies?

NASA Technical Reports Server (NTRS)

Vilas, Faith

1995-01-01

The U-B color has been suggested as a predictor of the presence of water of hydration on asteroids. Photometry from the Eight-Color Asteroid Survey (ECAS) was used to test this concept. An overlap in U-B color prevents this magnitude difference from distinguishing between surface material that was thermally processed at higher temperatures and surface material that was aqueously altered. Two tests of the presence of water of hydration using visible spectral region photometry failed to flag those few higher albedo M- and E-class asteroids having photometry that shows a 3.0-micrometers water of hydration absorption. These asteroids probably contain little or no oxidized iron in their surface material.

Identifying anthropogenic uranium compounds using soft X-ray near-edge absorption spectroscopy

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

Ward, Jesse D.; Bowden, Mark; Tom Resch, C.

2017-01-01

Uranium ores mined for industrial use are typically acid-leached to produce yellowcake and then converted into uranium halides for enrichment and purification. These anthropogenic chemical forms of uranium are distinct from their mineral counterparts. The purpose of this study is to use soft X-ray absorption spectroscopy to characterize several common anthropogenic uranium compounds important to the nuclear fuel cycle. Non-destructive chemical analyses of these compounds is important for process and environmental monitoring and X-ray absorption techniques have several advantages in this regard, including element-specificity, chemical sensitivity, and high spectral resolution. Oxygen K-edge spectra were collected for uranyl nitrate, uranyl fluoride,more » and uranyl chloride, and fluorine K-edge spectra were collected for uranyl fluoride and uranium tetrafluoride. Interpretation of the data is aided by comparisons to calculated spectra. These compounds have unique spectral signatures that can be used to identify unknown samples.« 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.

Geochemistry and microbiology at gas hydrate and mud volcano sites in the black sea

NASA Astrophysics Data System (ADS)

Drews, M.; Schmaljohann, R.; Wallmann, K.

2003-04-01

We present geochemical and microbiological results which were obtained from sediments at gas hydrate and mud volcano sites in the Sorokin Trough (northern Black Sea, south east of the Crimean peninsula) at water depths of about 1800 to 2100 m during the METEOR cruise 52-1. The surface near sub-bottom accumulations of gas hydrates (occuring at depths of several meters or less beneath the sea floor) in the Black Sea are associated with numerous mud volcanos. At stations we investigated gas hydrates occurred below 10 cm to 100 cm with a significant influence on the sediment biochemistry. Analyses revealed high methane concentrations, anoxic and sulfidic conditions, a steep sulfate gradient, carbonate precipitation, and high anaerobic methane oxidation rates. In proximity of the so called Odessa mud volcano one investigated sampling station showed maximum methane oxidation rates in the depth horizon of a firm 2 cm thick carbonate crust layer, adhered to by a bacterial mat. This observation is taken to indicate that the bacteria are causing or mediating the crust formation by their anaerobic methane oxidation metabolism. The station was further characterised by two layers of gas hydrate fragments and lenses below 1 m depth. A 2 to 4 cm thick carbonate crust with attached bacterial mat from a Yalta mud vulcano sample (2124 m water depth) was investigated under the scanning electron microscope. The stiff gelatinous mat showed a dense and morphologically uniform population of rod shaped bacteria with only a few nests of coccoid cells. Purified mat material exhibited anaerobic methane oxidation activity. These mats resemble the type previously found in the shallow NW methane seep area of the Black Sea, where it covers carbonate chimneys. Samples from two sites atop the summit of the active but flat-topped Dvurechenskii mud volcano were characterised by very high methane oxidation rates (up to 563 nmol/cm3/d) at the sediment surface. Strong pore water gradients of chloride, bromide, ammonium, methane, and temperature proved the existence of a rich upward flow of warm fluids from the deeper sediment. At both stations no carbonate crusts or bacterial mats were found. The lack of hemipelagic sediments and at the same time abundance of mud breccia gives ample evidence of the recency of the mud flow.

Temperature dependence of polyhedral cage volumes in clathrate hydrates

USGS Publications Warehouse

Chakoumakos, B.C.; Rawn, C.J.; Rondinone, A.J.; Stern, L.A.; Circone, S.; Kirby, S.H.; Ishii, Y.; Jones, C.Y.; Toby, B.H.

2003-01-01

The polyhedral cage volumes of structure I (sI) (carbon dioxide, methane, trimethylene oxide) and structure II (sII) (methane-ethane, propane, tetrahydrofuran, trimethylene oxide) hydrates are computed from atomic positions determined from neutron powder-diffraction data. The ideal structural formulas for sI and sII are, respectively, S2L6 ?? 46H2O and S16L???8 ?? 136H2O, where S denotes a polyhedral cage with 20 vertices, L a 24-cage, and L??? a 28-cage. The space-filling polyhedral cages are defined by the oxygen atoms of the hydrogen-bonded network of water molecules. Collectively, the mean cage volume ratio is 1.91 : 1.43 : 1 for the 28-cage : 24-cage : 20-cage, which correspond to equivalent sphere radii of 4.18, 3.79, and 3.37 A??, respectively. At 100 K, mean polyhedral volumes are 303.8, 227.8, and 158.8 A??3 for the 28-cage, 24-cage, and 20-cage, respectively. In general, the 20-cage volume for a sII is larger than that of a sI, although trimethylene oxide is an exception. The temperature dependence of the cage volumes reveals differences between apparently similar cages with similar occupants. In the case of trimethylene oxide hydrate, which forms both sI and sII, the 20-cages common to both structures contract quite differently. From 220 K, the sII 20-cage exhibits a smooth monotonic reduction in size, whereas the sI 20-cage initially expands upon cooling to 160 K, then contracts more rapidly to 10 K, and overall the sI 20-cage is larger than the sII 20-cage. The volumes of the large cages in both structures contract monotonically with decreasing temperature. These differences reflect reoriented motion of the trimethyelene oxide molecule in the 24-cage of sI, consistent with previous spectroscopic and calorimetric studies. For the 20-cages in methane hydrate (sI) and a mixed methane-ethane hydrate (sII), both containing methane as the guest molecule, the temperature dependence of the 20-cage volume in sII is much less than that in sI, but sII is overall larger in volume.

Morin hydrate augments phagocytosis mechanism and inhibits LPS induced autophagic signaling in murine macrophage.

PubMed

Jakhar, Rekha; Paul, Souren; Chauhan, Anil Kumar; Kang, Sun Chul

2014-10-01

Morin, a natural flavonoid that is the primary bioactive constituent of the family Moraceae, has been found to be associated with many therapeutic properties. In this study, we evaluated the immunomodulatory activities of increasing concentration of morin hydrate in vitro. Three different concentrations of morin hydrate (5, 10, and 15μM) were used to evaluate their effect on splenocyte proliferation, phagocytic activity of macrophages, cytokine secretion and complement inhibition. We also evaluated the role of morin hydrate on lipopolysaccharide (LPS) induced autophagy. Our study demonstrated that morin hydrate elicited a significant increase in splenocyte proliferation, phagocytic capacity and suppressed the production of cytokines and nitric oxide in activated macrophages. Humoral immunity measured by anti-complement activity showed an increase in inhibition of the complement system after the addition of morin hydrate, where morin hydrate at 15μM concentration induced a significant inhibition. Depending on our results, we can also conclude that morin hydrate protects macrophages from LPS induced autophagic cell death. Our findings suggest that morin hydrate represents a structurally diverse class of flavonoid and this structural variability can profoundly affect its cell-type specificity and its biological activities. Supplementation of immune cells with morin hydrate has an upregulating and immunoprotective effect that shows potential as a countermeasure to the immune dysfunction and suggests an interesting use in inflammation related diseases. Copyright © 2014 Elsevier B.V. All rights reserved.

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

Hydrogen sulfide (H2S) attenuates uranium-induced acute nephrotoxicity through oxidative stress and inflammatory response via Nrf2-NF-κB pathways.

PubMed

Zheng, Jifang; Zhao, Tingting; Yuan, Yan; Hu, Nan; Tang, Xiaoqing

2015-12-05

As an endogenous gaseous mediator, H2S exerts anti-oxidative, anti-inflammatory and cytoprotective effects in kidneys. This study was designed to investigate the protective effect of H2S against uranium-induced nephrotoxicity in adult SD male rats after in vivo effect of uranium on endogenous H2S formation was explored in kidneys. The levels of endogenous H2S and H2S-producing enzymes (CBS and CSE) were measured in renal homogenates from rats intoxicated by an intraperitoneally (i.p.) injection of uranyl acetate at a single dose of 2.5, 5 or 10 mg/kg. In rats injected i.p. with uranyl acetate (5 mg/kg) or NaHS (an H2S donor, 28 or 56 μmol/kg) alone or in combination, we determined biochemical parameters and histopathological alteration to assess kidney function, examined oxidative stress markers, and investigated Nrf2 and NF-κB pathways in kidney homogenates. The results suggest that uranium intoxication in rats decreased endogenous H2S generation as well as CBS and CSE protein expression. NaHS administration in uranium-intoxicated rats ameliorated the renal biochemical indices and histopathological effects, lowered MDA accumulation, and restored GSH level and anti-oxidative enzymes activities like SOD, CAT, GPx and GST. NaHS treatment in uranium-intoxicated rats activated uranium-inhibited protein expression and nuclear translocation of transcription factor Nrf2, which increased protein expression of downstream target-Nrf2 genes HO-1, NQO-1, GCLC, and TXNRD-1. NaHS administration in uranium-intoxicated rats inhibited uranium-induced nuclear translocation and phosphorylation of transcription factor κB/p65, which decreased protein expression of target-p65 inflammatory genes TNF-α, iNOS, and COX-2. Taken together, these data implicate that H2S can afford protection to rat kidneys against uranium-induced adverse effects through induction of antioxidant defense by activating Nrf2 pathway and reduction of inflammatory response by suppressing NF-κB pathway. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Nitric oxide scavengers differentially inhibit ammonia oxidation in ammonia-oxidizing archaea and bacteria.

PubMed

Sauder, Laura A; Ross, Ashley A; Neufeld, Josh D

2016-04-01

Differential inhibitors are important for measuring the relative contributions of microbial groups, such as ammonia-oxidizing bacteria (AOB) and ammonia-oxidizing archaea (AOA), to biogeochemical processes in environmental samples. In particular, 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl 3-oxide (PTIO) represents a nitric oxide scavenger used for the specific inhibition of AOA, implicating nitric oxide as an intermediate of thaumarchaeotal ammonia oxidation. This study investigated four alternative nitric oxide scavengers for their ability to differentially inhibit AOA and AOB in comparison to PTIO. Caffeic acid, curcumin, methylene blue hydrate and trolox were tested onNitrosopumilus maritimus, two unpublished AOA representatives (AOA-6f and AOA-G6) as well as the AOB representative Nitrosomonas europaea All four scavengers inhibited ammonia oxidation by AOA at lower concentrations than for AOB. In particular, differential inhibition of AOA and AOB by caffeic acid (100 μM) and methylene blue hydrate (3 μM) was comparable to carboxy-PTIO (100 μM) in pure and enrichment culture incubations. However, when added to aquarium sponge biofilm microcosms, both scavengers were unable to inhibit ammonia oxidation consistently, likely due to degradation of the inhibitors themselves. This study provides evidence that a variety of nitric oxide scavengers result in differential inhibition of ammonia oxidation in AOA and AOB, and provides support to the proposed role of nitric oxide as a key intermediate in the thaumarchaeotal ammonia oxidation pathway. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

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

Water-Rock Reactions on Non-Planetary Bodies in the Early Solar System

NASA Astrophysics Data System (ADS)

Zolotov, M. Y.

2005-12-01

Reactions of aqueous fluids with rocks shortly after formation of the solar system affected the oxidation states, mineralogy, organic speciation, ice composition, and surface/atmospheric chemistry of asteroids, icy satellites of giant plants, and possibly Kuiper belt objects. Water condensed as ice in the solar nebula, was incorporated into the composition of these bodies together with rocky components represented by extremely reduced and anhydrous nebular condensates (e.g., Fe-rich metal, forsterite, low-Ca pyroxene, troilite, Ca-Mg-Al oxides, phosphides), presolar grains (SiC, graphite, diamond, Al-, Mg-, Ti-oxides) and organic compounds and polymers. Radioactive decay of short-lived radionuclides on small bodies, and accretionary heat and decay of long-lived radionuclides on large bodies provided energy to melt ice. On smaller bodies, low gravity precluded separation of water from rocks and restricted fluid dynamics. On larger bodies, water was separated from descending rocks, limiting the duration of water-rock reactions. Competitive oxidation and hydration by water affected both inorganic and organic compounds in rocks. Oxidation of minerals led to formation of ferrous silicates, magnetite, pyrrhotite, Ni sulfides, Ni-rich metal alloys, chromite, phosphates, carbonates and sulfates. Hydration caused formation of phyllosilicates (serpentine, chlorites, smectite clays, amphiboles, and micas), hydroxides, and hydrated sulfides and salts. High water/rock ratios, elevated temperatures and low pressures favored oxidation. Low temperatures supported hydration. In some icy satellites (Europa, Ganymede) high water content and hydrothermal processes during differentiation may have caused profound oxidation leading to carbonates and even sulfates. Since water was the only early oxidizing agent, the elevated oxidation state of Io implies its early aqueous history. Hydrogen was produced in all oxidation reactions and preferentially separated into the gas phase. Escape of H2 into space promoted oxidation, consistent with the high oxidation state of highly porous CI and CM carbonaceous chondrites. Low porosity and permeability, filling of pore space with secondary minerals, and sealing of outer zones with ice restricted H2 escape, retarded some oxidation reactions and caused incomplete reduction of minerals formed earlier by oxidation. For example, magnetite was partially converted to ferrous silicates. The limited oxidation and signs of reduction in some meteorite types (unequilibrated ordinary and CV3 carbonaceous chondrites) is consistent with low amounts of incorporated water ice and low porosity of parent asteroids. Although prolonged heating of bodies caused dehydration and some reduction, water-rock reactions led to net oxidation of primary rocky components, consistent with the elevated oxidation states of metamorphosed chondrites and Io. Interaction of water with organic compounds and carbon grains caused disproportionation of carbon leading to O-bearing organic compounds and CO2, as well as to hydrogenated organic compounds and methane. In small bodies, organic matter was only partially altered. In some icy satellites, prolonged reactions and elevated pressures favored formation of light hydrocarbons and methane, consistent with observations (e.g., Titan, Triton). In most bodies, net oxidation of organic compounds can be attributed to preservation of CO2 and O-bearing organics in solution, ices and carbonates, and escape of H2 formed through oxidation reactions.

Selective Encaging of N2O in N2O-N2 Binary Gas Hydrates via Hydrate-Based Gas Separation.

PubMed

Yang, Youjeong; Shin, Donghoon; Choi, Seunghyun; Woo, Yesol; Lee, Jong-Won; Kim, Dongseon; Shin, Hee-Young; Cha, Minjun; Yoon, Ji-Ho

2017-03-21

The crystal structure and guest inclusion behaviors of nitrous oxide-nitrogen (N 2 O-N 2 ) binary gas hydrates formed from N 2 O/N 2 gas mixtures are determined through spectroscopic analysis. Powder X-ray diffraction results indicate that the crystal structure of all the N 2 O-N 2 binary gas hydrates is identified as the structure I (sI) hydrate. Raman spectra for the N 2 O-N 2 binary gas hydrate formed from N 2 O/N 2 (80/20, 60/40, 40/60 mol %) gas mixtures reveal that N 2 O molecules occupy both large and small cages of the sI hydrate. In contrast, there is a single Raman band of N 2 O molecules for the N 2 O-N 2 binary gas hydrate formed from the N 2 O/N 2 (20/80 mol %) gas mixture, indicating that N 2 O molecules are trapped in only large cages of the sI hydrate. From temperature-dependent Raman spectra and the Predictive Soave-Redlich-Kwong (PSRK) model calculation, we confirm the self-preservation of N 2 O-N 2 binary gas hydrates in the temperature range of 210-270 K. Both the experimental measurements and the PSRK model calculations demonstrate the preferential occupation of N 2 O molecules rather than N 2 molecules in the hydrate cages, leading to a possible process for separating N 2 O from gas mixtures via hydrate formation. The phase equilibrium conditions, pseudo-pressure-composition (P-x) diagram, and gas storage capacity of N 2 O-N 2 binary gas hydrates are discussed in detail.

On the mechanical stability of uranyl peroxide hydrates: Implications for nuclear fuel degradation

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

Weck, Philippe F.; Kim, Eunja; Buck, Edgar C.

The mechanical properties and stability of studtite, (UO2)(O2)(H2O)2·2H2O, and metastudtite, (UO2)(O2)(H2O)2, two important corrosion phases observed on spent nuclear fuel exposed to water, have been investigated using density functional perturbation theory. While (UO2)(O2)(H2O)2 satisfies the necessary and sufficient Born criteria for mechanical stability, (UO2)(O2)(H2O)2·2H2O is found to be mechanically metastable, which might be the underlying cause of the irreversibility of the studtite to metastudtite transformation. According to Pugh’s and Poisson’s ratios and the Cauchy pressure, both phases are considered ductile and shear modulus is the parameter limiting their mechanical stability. Debye temperatures of 294 and 271 K are predicted formore » polycrystalline (UO2)(O2)(H2O)2·2H2O and (UO2)(O2)(H2O)2, suggesting a lower micro-hardness of metastudtite.« less

On the mechanical stability of uranyl peroxide hydrates: Implications for nuclear fuel degradation

DOE PAGES

Weck, Philippe F.; Kim, Eunja; Buck, Edgar C.

2015-09-11

The mechanical properties and stability of studtite, (UO 2)(O 2)(H 2O) 2·2H 2O, and metastudtite, (UO 2)(O 2)(H 2O) 2, two important corrosion phases observed on spent nuclear fuel exposed to water, have been investigated using density functional perturbation theory. While (UO 2)(O 2)(H 2O) 2 satisfies the necessary and sufficient Born criteria for mechanical stability, (UO 2)(O 2)(H 2O) 2·2H 2O is found to be mechanically metastable, which might be the underlying cause of the irreversibility of the studtite to metastudtite transformation. According to Pugh's and Poisson's ratios and the Cauchy pressure, both phases are considered ductile and shearmore » modulus is the parameter limiting their mechanical stability. Furthermore, debye temperatures of 294 and 271 K are predicted for polycrystalline (UO 2)(O 2)(H 2O) 2·2H 2O and (UO 2)(O 2)(H 2O) 2, suggesting a lower micro-hardness of metastudtite.« 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

Concrete with steel furnace slag and fractionated reclaimed asphalt pavement.

DOT National Transportation Integrated Search

2014-09-01

Steel furnace slag (SFS) is an industrial by-product material that can contain free calcium oxide (CaO) and free magnesium oxide (MgO), both : of which can cause significant expansion when hydrated. SFS aggregates are therefore not commonly used in c...

SURFACE REACTIONS OF OXIDES OF SULFUR

EPA Science Inventory

Surface reactions of several sulfur-containing molecules have been studied in order to understand the mechanism by which sulfate ions are formed on atmospheric aerosols. At 25C the heterogeneous oxidation of SO2 by NO2 to sulfuric acid and sulfate ions occurred on hydrated silica...

IMPROVED MAGNESIUM OXIDE SLIP CASTING METHOD

DOEpatents

Stoddard, S.D.; Nuckolls, D.E.

1963-12-31

A process for making an aqueous magnesium oxide slip casting slurry comprising the steps of mixing finely ground fused magnesium oxide with water, milling the slurry for at least 30 hours at a temperature of 2-10 deg C (the low temperature during milling inhibiting the formation of hydrated magnesium oxide), discharging the slurry from the mill, adding hydrochloric acid as a deflocculent, and adding a scum inhibitor is presented. (AEC)

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

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

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.

Properties of Cement Mortar and Ultra-High Strength Concrete Incorporating Graphene Oxide Nanosheets

PubMed Central

Ouyang, Dong

2017-01-01

In this work, the effect of graphene oxide nanosheet (GONS) additives on the properties of cement mortar and ultra-high strength concrete (UHSC) is reported. The resulting GONS-cement composites were easy to prepare and exhibited excellent mechanical properties. However, their fluidity decreased with increasing GONS content. The UHSC specimens were prepared with various amounts of GONSs (0–0.03% by weight of cement). Results indicated that using 0.01% by weight of cement GONSs caused a 7.82% in compressive strength after 28 days of curing. Moreover, adding GONSs improved the flexural strength and deformation ability, with the increase in flexural strength more than that of compressive strength. Furthermore, field-emission scanning electron microscopy (FE-SEM) was used to observe the morphology of the hardened cement paste and UHSC samples. FE-SEM observations showed that the GONSs were well dispersed in the matrix and the bonding of the GONSs and the surrounding cement matrix was strong. Furthermore, FE-SEM observation indicated that the GONSs probably affected the shape of the cement hydration products. However, the growth space for hydrates also had an important effect on the morphology of hydrates. The true hydration mechanism of cement composites with GONSs needs further study. PMID:28726750

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.

The influence of iridium chemical oxidation state on the performance and durability of oxygen evolution catalysts in PEM electrolysis

NASA Astrophysics Data System (ADS)

Siracusano, S.; Baglio, V.; Grigoriev, S. A.; Merlo, L.; Fateev, V. N.; Aricò, A. S.

2017-10-01

Nanosized Ir-black (3 nm) and Ir-oxide (5 nm) oxygen evolution electrocatalysts showing high performance in polymer electrolyte membrane (PEM) water electrolysis based on Aquivion® short-side chain ionomer membrane are investigated to understand the role of the Ir oxidation state on the electrocatalytic activity and stability. Despite the smaller mean crystallite size, the Ir-black electrocatalyst shows significantly lower initial performance than the Ir-oxide. During operation at high current density, the Ir-black shows a decrease of cell potential with time whereas the Ir-oxide catalyst shows increasing cell potential resulting in a degradation rate of about 10 μV/h, approaching 1000 h. The unusual behaviour of the Ir-black results from the oxidation of metallic Ir to IrOx. The Ir-oxide catalyst shows instead a hydrated structure on the surface and a negative shift of about 0.5 eV for the Ir 4f binding energy after 1000 h electrolysis operation. This corresponds to the formation of a sub-stoichiometric Ir-oxide on the surface. These results indicate that a hydrated IrO2 with high oxidation state on the surface is favourable in decreasing the oxygen evolution overpotential. Modifications of the Ir chemical oxidation state during operation can affect significantly the catalytic activity and durability of the electrolysis system.

Respirable Uranyl-Vanadate Containing Particulate Matter Derived from a Legacy Uranium Mine Site Exhibits Potentiated Cardiopulmonary Toxicity.

PubMed

Zychowski, Katherine E; Kodali, Vamsi; Harmon, Molly; Tyler, Christina; Sanchez, Bethany; Ordonez Suarez, Yoselin; Herbert, Guy; Wheeler, Abigail; Avasarala, Sumant; Cerrato, José M; Kunda, Nitesh K; Muttil, Pavan; Shuey, Chris; Brearley, Adrian; Ali, Abdul-Mehdi; Lin, Yan; Shoeb, Mohammad; Erdely, Aaron; Campen, Matthew J

2018-04-05

Exposure to windblown particulate matter (PM) arising from legacy uranium (U) mine sites in the Navajo Nation may pose a human health hazard due to their potentially high metal content, including U and vanadium (V). To assess the toxic impact of PM derived from Claim 28 (a priority U mine) compared to background PM, and consider the putative role of metal species U and V. Two representative sediment samples from Navajo Nation sites (Background PM and Claim 28 PM) were obtained, characterized in terms of chemistry and morphology, and fractioned to the respirable (≤10μm) fraction. Mice were dosed with either PM sample, uranyl acetate or vanadyl sulfate via aspiration (100µg), with assessments of pulmonary and vascular toxicity 24h later. PM samples were also examined for in vitro effects on cytotoxicity, oxidative stress, phagocytosis, and inflammasome induction. Claim 28 PM10 was highly enriched with U and V and exhibited a unique nanoparticle ultrastructure compared to background PM10. Claim 28 PM10 exhibited enhanced pulmonary and vascular toxicity relative to background PM10. Both U and V exhibited complementary pulmonary inflammatory potential, with U driving a classical inflammatory cytokine profile (elevated IL-1β, TNFα, KC/GRO) while V preferentially induced a different cytokine pattern (elevated IL-5, IL-6, IL-10). Claim 28 PM10 was more potent than background PM10 in terms of in vitro cytotoxicity, impairment of phagocytosis, and oxidative stress responses. Resuspended PM10 derived from U mine waste exhibit greater cardiopulmonary toxicity than background dusts. Rigorous exposure assessment is needed to gauge the regional health risks imparted by these unremediated sites.

Uranium speciation in Fernald soils. Progress report, January 1--May 31, 1992

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

Morris, D.E.; Conradson, S.D.; Tait, C.D.

1992-05-31

This report details progress made from January 1 to May 31, 1992 in this analytical support task to determine the speciation of uranium in contaminated soil samples from the Fernald Environmental Management Project site under the auspices of the Uranium in Soils Integrated Demonstration funded through the US DOE`s Office of Technology Development. The authors` efforts have focused on characterization of soil samples collected by S.Y. Lee (Oak Ridge National Laboratory) from five locales at the Fernald site. These were chosen to sample a broad range of uranium source terms. On the basis of x-ray absorption spectroscopy data, they havemore » determined that the majority of uranium (> 80--90%) exists in the hexavalent oxidation state for all samples examined. This is a beneficial finding from the perspective of remediation, because U(VI) species are more soluble in general than uranium species in other oxidation states. Optical luminescence data from many of the samples show the characteristic structured yellow-green emission from the uranyl (UO{sub 2}{sup 2+}) moiety. The luminescence data also suggest that much of the uranium in these soils is present as well-crystallized UO{sub 2}{sup 2+} species. Some clear spectroscopic distinctions have been noted for several samples that illustrate significant differences in the speciation (1) from site to site, (2) within different horizons at the same site, and (3) within different size fractions of the soils in the same horizon at the same site. This marked heterogeneity in uranyl speciation suggests that several soil washing strategies may be necessary to reduce the total uranium concentrations within these soils to regulatory limits.« less

Detection of biological uranium reduction using magnetic resonance.

PubMed

Vogt, Sarah J; Stewart, Brandy D; Seymour, Joseph D; Peyton, Brent M; Codd, Sarah L

2012-04-01

The conversion of soluble uranyl ions (UO₂²⁺) by bacterial reduction to sparingly soluble uraninite (UO₂(s)) is being studied as a way of immobilizing subsurface uranium contamination. Under anaerobic conditions, several known types of bacteria including iron and sulfate reducing bacteria have been shown to reduce U (VI) to U (IV). Experiments using a suspension of uraninite (UO₂(s)) particles produced by Shewanella putrefaciens CN32 bacteria show a dependence of both longitudinal (T₁) and transverse (T₂) magnetic resonance (MR) relaxation times on the oxidation state and solubility of the uranium. Gradient echo and spin echo MR images were compared to quantify the effect caused by the magnetic field fluctuations (T*₂) of the uraninite particles and soluble uranyl ions. Since the precipitate studied was suspended in liquid water, the effects of concentration and particle aggregation were explored. A suspension of uraninite particles was injected into a polysaccharide gel, which simulates the precipitation environment of uraninite in the extracellular biofilm matrix. A reduction in the T₂ of the gel surrounding the particles was observed. Tests done in situ using three bioreactors under different mixing conditions, continuously stirred, intermittently stirred, and not stirred, showed a quantifiable T₂ magnetic relaxation effect over the extent of the reaction. Copyright © 2011 Wiley Periodicals, Inc.

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.

SIMULTANEOUS CONTROL OF HG(0), SO2, AND NOX BY NOVEL OXIDIZED CALCIUM-BASED SORBENTS

EPA Science Inventory

The paper gives results of an investigation of two classes of calcium (Ca)-based sorbents (hydrated limes and silicate compounds). {NOTE: Efforts to develop multipollutant control strategies have demonstrated that adding certain oxidants to different classes of Ca-based sorbents ...

SIMULTANEOUS CONTROL OF HGO, SO2, AND NOX BY NOVEL OXIDIZED CALCIUM-BASED SORBENTS

EPA Science Inventory

The paper gives results of an investigation of two classes of calcium (Ca)-based sorbents (hydrated limes and silicate compounds). (NOTE: Efforts to develop multipollutant control strategies have demonstrated that adding certain oxidants to different classes of Ca-based sorbents...

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.

15N and 31P solid-state NMR study of transmembrane domain alignment of M2 protein of influenza A virus in hydrated cylindrical lipid bilayers confined to anodic aluminum oxide nanopores.

PubMed

Chekmenev, Eduard Y; Hu, Jun; Gor'kov, Peter L; Brey, William W; Cross, Timothy A; Ruuge, Andres; Smirnov, Alex I

2005-04-01

This communication reports the first example of a high resolution solid-state 15N 2D PISEMA NMR spectrum of a transmembrane peptide aligned using hydrated cylindrical lipid bilayers formed inside nanoporous anodic aluminum oxide (AAO) substrates. The transmembrane domain SSDPLVVA(A-15N)SIIGILHLILWILDRL of M2 protein from influenza A virus was reconstituted in hydrated 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine bilayers that were macroscopically aligned by a conventional micro slide glass support or by the AAO nanoporous substrate. 15N and 31P NMR spectra demonstrate that both the phospholipids and the protein transmembrane domain are uniformly aligned in the nanopores. Importantly, nanoporous AAO substrates may offer several advantages for membrane protein alignment in solid-state NMR studies compared to conventional methods. Specifically, higher thermal conductivity of aluminum oxide is expected to suppress thermal gradients associated with inhomogeneous radio frequency heating. Another important advantage of the nanoporous AAO substrate is its excellent accessibility to the bilayer surface for exposure to solute molecules. Such high accessibility achieved through the substrate nanochannel network could facilitate a wide range of structure-function studies of membrane proteins by solid-state NMR.

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.

Dissolution of uranophane: An AFM, XPS, SEM and ICP study

NASA Astrophysics Data System (ADS)

Schindler, Michael; Freund, Michael; Hawthorne, Frank C.; Burns, Peter C.; Maurice, Patricia A.

2009-05-01

Dissolution experiments on single crystals of uranophane and uranophane-β, Ca(H 2O) 5[(UO 2)(SiO 3(OH)] 2, from the Shinkolobwe mine of the Democratic Republic of Congo, were done in an aqueous HCl solution of pH 3.5 for 3 h, in HCl solutions of pH 2 for 5, 10 and 30 min, and in Pb 2+-, Ba-, Sr-, Ca- and Mg-HCl solutions of pH 2 for 30 min. The basal surfaces of the treated uranophane crystals were examined using atomic-force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Solutions after dissolution experiments on single crystals and synthetic powders were analysed with inductively coupled plasma-optical emission spectroscopy (ICP-OES) and mass spectroscopy (ICP-MS). The morphology of the observed etch pits (measured by AFM) were compared to the morphology, predicted on the basis of the bond-valence deficiency of polyhedron chains along the edges of the basal surface. Etch pits form in HCl solutions of pH 2. Their decrease in depth with the duration of the dissolution experiment is explained with the stepwave dissolution model, which describes the lowering of the surrounding area of an etch pit with continuous waves of steps emanated from the etch pit into the rest of the crystal surface. Hillocks form in an HCl solution of pH 3.5, and the chemical composition of the surface (as indicated by XPS) shows that these hillocks are the result of the precipitation of a uranyl-hydroxy-hydrate phase. Well-orientated hillocks form on the surface of uranophane in a SrCl 2-HCl solution of pH 2. They are part of an aged silica coating of composition Si 2O 2(OH) 4(H 2O) n. An amorphous layer forms on the surface of uranophane in a MgCl 2-HCl solution of pH 2, which has a composition and structure similar to silicic acid. Small crystallites of uranyl-hydroxy-hydrate phases form on the surface of uranophane after treatment in Pb(NO 3) 2-HCl and BaCl 2-HCl solutions of pH 2. Dissolution experiments on synthetic uranophane powders show that in the early stage of the experiments, the dissolution rate of uranophane increase in the sequence Pb(NO 3) 2-HCl < BaCl 2-HCl < CaCl 2-HCl < HCl < SrCl 2-HCl < MgCl 2-HCl, indicating that the dissolution of uranophane is more enhanced in solutions containing divalent cations of small ionic radii and high Lewis acidity (Mg, MgCl +).

Development of Impregnated Agglomerate Pelletization (IAP) process for fabrication of (Th,U)O 2 mixed oxide pellets

NASA Astrophysics Data System (ADS)

Khot, P. M.; Nehete, Y. G.; Fulzele, A. K.; Baghra, Chetan; Mishra, A. K.; Afzal, Mohd.; Panakkal, J. P.; Kamath, H. S.

2012-01-01

Impregnated Agglomerate Pelletization (IAP) technique has been developed at Advanced Fuel Fabrication Facility (AFFF), BARC, Tarapur, for manufacturing (Th, 233U)O 2 mixed oxide fuel pellets, which are remotely fabricated in hot cell or shielded glove box facilities to reduce man-rem problem associated with 232U daughter radionuclides. This technique is being investigated to fabricate the fuel for Indian Advanced Heavy Water Reactor (AHWR). In the IAP process, ThO 2 is converted to free flowing spheroids by powder extrusion route in an unshielded facility which are then coated with uranyl nitrate solution in a shielded facility. The dried coated agglomerate is finally compacted and then sintered in oxidizing/reducing atmosphere to obtain high density (Th,U)O 2 pellets. In this study, fabrication of (Th,U)O 2 mixed oxide pellets containing 3-5 wt.% UO 2 was carried out by IAP process. The pellets obtained were characterized using optical microscopy, XRD and alpha autoradiography. The results obtained were compared with the results for the pellets fabricated by other routes such as Coated Agglomerate Pelletization (CAP) and Powder Oxide Pelletization (POP) route.

Surface acid-base properties and hydration/dehydration mechanisms of aluminum (hydr)oxides.

PubMed

Yang, Xiaofang; Sun, Zhongxi; Wang, Dongsheng; Forsling, Willis

2007-04-15

In this paper, surface physiochemical properties of three typical aluminas, gamma-Al(OH)3, gamma-Al2O3, and alpha-Al2O3, were investigated by means of XRD, SEM, TEM, BET surface area, TG/DTA, and potentiometric titration techniques. Based on the titration data, surface protonation and deprotonation constants were determined using the constant capacitance model (CCM). The emphasis of this research was laid on the comparison of the crystal structure, surface hydration/dehydration and acid-base properties of these three typical alumina minerals. The calculation results revealed that the surface acidity of the aluminas is in the order of alpha-Al2O3>gamma-Al(OH)3>gamma-Al2O3 after being hydrated for 1 h. The correlation between the hydration/dehydration mechanisms of alumina and its acid/base properties is discussed.

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.

Investigation of Silica-Supported Vanadium Oxide Catalysts by High-Field 51 V Magic-Angle Spinning NMR

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

Jaegers, Nicholas R.; Wan, Chuan; Hu, Mary Y.

Supported V2O5/SiO2 catalysts were studied using solid state 51V MAS NMR at a sample spinning rate of 36 kHz and at a magnetic field of 19.975 T for a better understanding of the coordination of the vanadium oxide as a function of environmental conditions . Structural transformations of the supported vanadium oxide species between the catalyst in the dehydrated state and hydrated state under an ambient environment were revisited to examine the degree of oligomerization and the effect of water. The experimental results indicate the existence of a single dehydrated surface vanadium oxide species that resonates at -675 ppm andmore » two vanadium oxide species under ambient conditions that resonate at -566 and -610 ppm, respectively. No detectable structural difference was found as a function of vanadium oxide loading on SiO2 (3% V2O5/SiO2 and 8% V2O5/SiO2). Quantum chemistry simulations of the 51V NMR chemical shifts on predicted surface structures were used as an aide in understanding potential surface vanadium oxide species on the silica support. The results suggest the formation of isolated surface VO4 units for the dehydrated catalysts with the possibility of dimer and cyclic trimer presence. The absence of bridging V-O-V vibrations (~200-300 cm-1) in the Raman spectra [Gao et al. J. Phys. Chem. B 1998, 102, 10842-10852], however, indicates that the isolated surface VO4 sites are the dominant dehydrated surface vanadia species on silica. Upon exposure to water, hydrolysis of the bridging V-O-Si bonds is most likely responsible for the decreased electron shielding experienced by vanadium. No indicators for the presence of hydrated decavanadate clusters or hydrated vanadia gels previously proposed in the literature were detected in this study.« less

SOLVENT-FREE REDUCTION OF AROMATIC NITRO COMPOUNDS WITH ALUMINA-SUPPORTED HYDRAZINE UNDER MICROWAVE IRRADIATION

EPA Science Inventory

In a solvent-free microwave-expedited process, aromatic nitro compounds are readily reduced to the corresponding amino compounds in good yield with hydrazine hydrate supported on alumina in presence of FeCl3, 6H2), Fe(III) oxide hydroxide or Fe(III) oxides.

Sivelestat sodium hydrate improves post-traumatic knee osteoarthritis through nuclear factor-κB in a rat model.

PubMed

Yu, Xiaofeng; Zhao, Lijun; Yu, Zhiping; Yu, Changzheng; Bi, Jianfei; Sun, Binglong; Cong, Haibo

2017-08-01

As a specific inhibitor of neutrophil elastase, sivelestat sodium hydrate has primarily been used in the treatment of acute lung injury caused by various factors since its approval in 2002. Sivelestat sodium hydrate also improves post-traumatic knee osteoarthritis (KOA), although its underlying mechanisms of action have yet to be elucidated. The aim of the current study was to determine if sivelestat sodium hydrate improves post-traumatic KOA through nuclear factor (NF)-κB in a rat model. Treatment with sivelestat sodium hydrate significantly inhibited the induction of structural changes and significantly increased the vertical episode count and ipsilateral static weight bearing of the joint in KOA rats (all P<0.01). Sivelestat sodium hydrate significantly inhibited tumor necrosis factor-α and interleukin-6 production, serum nitrite levels, inducible nitric oxide synthase protein expression and high mobility group box 1 (HMGB1) secretion in KOA rats compared with the model group (all P<0.01). Sivelestat sodium hydrate also significantly suppressed p50/p65 DNA binding activity and NF-κB and phosphorylated inhibitor of κB protein expression in the joints of KOA rats compared with the model group (all P<0.01). These results suggest that sivelestat sodium hydrate improves post-traumatic KOA through HMGB1 and NF-κB in rats.

Sivelestat sodium hydrate improves post-traumatic knee osteoarthritis through nuclear factor-κB in a rat model

PubMed Central

Yu, Xiaofeng; Zhao, Lijun; Yu, Zhiping; Yu, Changzheng; Bi, Jianfei; Sun, Binglong; Cong, Haibo

2017-01-01

As a specific inhibitor of neutrophil elastase, sivelestat sodium hydrate has primarily been used in the treatment of acute lung injury caused by various factors since its approval in 2002. Sivelestat sodium hydrate also improves post-traumatic knee osteoarthritis (KOA), although its underlying mechanisms of action have yet to be elucidated. The aim of the current study was to determine if sivelestat sodium hydrate improves post-traumatic KOA through nuclear factor (NF)-κB in a rat model. Treatment with sivelestat sodium hydrate significantly inhibited the induction of structural changes and significantly increased the vertical episode count and ipsilateral static weight bearing of the joint in KOA rats (all P<0.01). Sivelestat sodium hydrate significantly inhibited tumor necrosis factor-α and interleukin-6 production, serum nitrite levels, inducible nitric oxide synthase protein expression and high mobility group box 1 (HMGB1) secretion in KOA rats compared with the model group (all P<0.01). Sivelestat sodium hydrate also significantly suppressed p50/p65 DNA binding activity and NF-κB and phosphorylated inhibitor of κB protein expression in the joints of KOA rats compared with the model group (all P<0.01). These results suggest that sivelestat sodium hydrate improves post-traumatic KOA through HMGB1 and NF-κB in rats. PMID:28810618

Chloral hydrate for sedation of children with asthma during dental treatment.

PubMed

Abdulhamid, I; Tremblay, M; Stenger, J; Tutag Lehr, V

2016-06-01

We hypothesised that chloral hydrate is safe and effective for sedation during dental treatments for children with mild asthma. We evaluated the safety and efficacy of chloral hydrate by measuring changes in heart rate (HR), transcutaneous oxygen saturation, (SpO2), asthma score, behaviour, types and frequency of adverse reactions associated with chloral hydrate were assessed throughout treatment. Children (<10 years old) with mild asthma undergoing dental treatments received a single 65 mg/kg oral dose of chloral hydrate liquid 1 hour prior to treatment in an open label trial. Heart rate (HR), SpO2, asthma score, behaviour, types and frequency of adverse reactions associated with chloral hydrate were assessed throughout treatment. Asthma score was obtained before and after treatment. Thirty minutes after treatment, SpO2, HR, and level of consciousness was assessed. Twenty four children were enrolled and 92% (22/24) recovered from sedation without respiratory depression. Two experienced mild respiratory depression related to chloral hydrate. Asthma was not a contributing factor as they did not experience wheezing, cough, tachypnoea, or retractions. Inhaled nitrous oxide supplemented chloral hydrate sedation in 63% (15/24) children to achieve effective cooperation. Three children had a SpO2 <95% (2 during treatment, 1 during recovery). Chloral hydrate 65 mg/kg administered a as single oral dose appears to be safe with respect to disease exacerbation for children with mild asthma undergoing dental treatment. Due to ineffective sedation and mild respiratory depression associated with chloral hydrate, newer, easily titrated medications, such as midazolam, may offer advantages.

Why we need detailed visible-range spectral data on Kuiper belt objects?

NASA Astrophysics Data System (ADS)

Busarev, V. V.

2001-05-01

Our understanding of Kuiper belt objects (KBOs)' nature may be based on two general scenarios of their origin. First, they could result from early accretional phases of the Solar System ``in situ". Then they are probably the most primitive and unprocessed bodies among known and should be mostly icy, with a very low content of silicate component. Second, a considerable portion of them (if not a majority) might have been thrown by Jupiter and other giant planets from their zones of accumulation. If so, they could include much more silicates (possibly up to 40%). To check the suppositions we need high-resolution visible and near-infrared spectral data on Centaurs (as possible `fugitives' from the Kuiper belt) and the KBOs. Because of faintness of the objects their physicochemical properties remain still little-known. Visible-range observations of the bodies by means of a spacecraft approaching to the belt could much help in solving the problem. Visible-infrared spectrophotometric observations of the objects showed a considerable diversity among them (Jewitt D. & J. Luu, 1998, Astron. J., 115, 1667-1670). It hints at a diversity in content of their matter. Spectral features of ices could not probably dominate in the visible range spectra of silicate-bearing KBOs. Reflectance spectra of principal gases' frosts are mainly flat and featureless in the range (Wagner J. K. et al., 1987, Icarus, 69, 14-28). Besides, silicates of KBOs are probably oxidized and hydrated to a high extent. Highly hydrated main-belt C-class asteroids have absorption bands at 0.43 and 0.6-0.8 microns (up to about 5%) (Vilas F. & M. J. Gaffey, 1989, Science, 246, 790-792 and Vilas F. et al., 1993, Icarus, 102, 225-231). Similar spectral features attributed to oxidized and hydrated silicates were also found on many M- and S-asteroids (e. g., Busarev V. V., 2001, LPSC XXXII, abstract 1927). The absorption bands are interpreted as caused by electronic processes in a bulk of oxidized silicates and hydrated clay minerals including structural OH-groups. Thus, the absorption features may be considered as indicators of a presence of oxidized and/or hydrated silicates on a solid body regardless of its position in the Solar System. For these reasons we have started visible-range spectroscopic observations of Centaurs and the KBOs on Russian 6-m telescope.

Sensitivity of the global submarine hydrate inventory to scenarios of future climate change

NASA Astrophysics Data System (ADS)

Hunter, S. J.; Goldobin, D. S.; Haywood, A. M.; Ridgwell, A.; Rees, J. G.

2013-04-01

The global submarine inventory of methane hydrate is thought to be considerable. The stability of marine hydrates is sensitive to changes in temperature and pressure and once destabilised, hydrates release methane into sediments and ocean and potentially into the atmosphere, creating a positive feedback with climate change. Here we present results from a multi-model study investigating how the methane hydrate inventory dynamically responds to different scenarios of future climate and sea level change. The results indicate that a warming-induced reduction is dominant even when assuming rather extreme rates of sea level rise (up to 20 mm yr-1) under moderate warming scenarios (RCP 4.5). Over the next century modelled hydrate dissociation is focussed in the top ˜100m of Arctic and Subarctic sediments beneath <500m water depth. Predicted dissociation rates are particularly sensitive to the modelled vertical hydrate distribution within sediments. Under the worst case business-as-usual scenario (RCP 8.5), upper estimates of resulting global sea-floor methane fluxes could exceed estimates of natural global fluxes by 2100 (>30-50TgCH4yr-1), although subsequent oxidation in the water column could reduce peak atmospheric release rates to 0.75-1.4 Tg CH4 yr-1.

CONTINUOUS PRECIPITATION METHOD FOR CONVERSION OF URANYL NITRATE TO URANIUM HEXAFLUORIDE

DOEpatents

Reinhart, G.M.; Collopy, T.J.

1962-11-13

A continuous precipitation process is given for converting a uranyl nitrate solution to uranium tetrafluoride. A stream of the uranyl nitrate solution and a stream of an aqueous ammonium hydroxide solution are continuously introduced into an agitated reaction zone maintained at a pH of 5.0 to 6.5. Flow rates are adjusted to provide a mean residence time of the resulting slurry in the reaction zone of at least 30 minutes. After a startup period of two hours the precipitate is recovered from the effluent stream by filtration and is converted to uranium tetrafluoride by reduction to uranium dioxide with hydrogen and reaction of the uranium dioxide with anhydrous hydrogen fluoride. (AEC)

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

Microbial mats in the Black Sea that anaerobically oxidise methane

NASA Astrophysics Data System (ADS)

Nauhaus, K.; Knittel, K.; Krüger, M.; Boetius, A.; Michaelis, W.; Widdel, F.

2003-04-01

Reef-forming microbial mats were recovered from methane seeps in anoxic waters of the northwestern Black Sea (BS) shelf. The microbial mats consist mainly of archaea (ANME-1 cluster) and sulfate-reducing bacteria (Desulfosarcina/Desulfococcus group). Laboratory incubations with homogenized subsamples of the mats revealed their ability for the anaerobic oxidation of methane (AOM). The phylogentic relationship of the sulfate reducing partner is the same as in the AOM consortia studied in sediment samples from a methane hydrate area (Hydrate Ridge (HR), Oregon, USA (1,2)). The archaeal partner however belongs to a different cluster than in the HR samples (ANME-2). Methane oxidation is coupled to sulfate reduction in a 1:1 stoichiometry. Elevated methane partial pressures (0.1 to 1.1 MPa) increased the sulfate reduction rates in the Black Sea samples only two-fold in contrast to 5-fold in HR samples. The optimal temperature for the BS samples is between 10 and 25^oC. In both samples AOM was not taking place if typical inhibitors for sulfate-reduction or methanogenesis were added, thus indicating a syntrophic relationship between the partner organisms. The intermediate that is exchanged between the methane oxidizing archaea and the sulfate-reducing bacterium is still unknown. Additions of the possible intermediates (Acetate, Formate, Hydrogen) did not result in higher sulfate reduction rates in the absence of methane. (1) Boetius, A. et al. (2000) A marine microbial consortium apparently mediating anaerobic oxidation of methane. Nature. 407: 623--626 (2) Nauhaus, K., Boetius, A., Krüger, M., Widdel, F. (2002) In vitro demonstration of anaerobic oxidation of methane coupled to sulphate reduction in sediment from a marine gas hydrate area. Environ. Microbiol. 4 (5): 296--305

Molecular and dissociative adsorption of DMMP, Sarin and Soman on dry and wet TiO2(110) using density functional theory

NASA Astrophysics Data System (ADS)

Quintero, Yenny Cardona; Nagarajan, Ramanathan

2018-09-01

Titania, among the metal oxides, has shown promising characteristics for the adsorption and decontamination of chemical warfare nerve agents, due to its high stability and rapid decomposition rates. In this study, the adsorption energy and geometry of the nerve agents Sarin and Soman, and their simulant dimethyl methyl phosphonate (DMMP) on TiO2 rutile (110) surface were calculated using density functional theory. The molecular and dissociative adsorption of the agents and simulant on dry as well as wet metal oxide surfaces were considered. For the wet system, computations were done for the cases of both molecularly adsorbed water (hydrated conformation) and dissociatively adsorbed water (hydroxylated conformation). DFT calculations show that dissociative adsorption of the agents and simulant is preferred over molecular adsorption for both dry and wet TiO2. The dissociative adsorption on hydrated TiO2 shows higher stability among the different configurations considered. The dissociative structure of DMMP on hydrated TiO2 (the most stable one) was identified as the dissociation of a methyl group and its adsorption on the TiO2 surface. For the nerve agents Sarin and Soman on hydrated TiO2 the dissociative structure was by the dissociation of the F atom from the molecule and its interaction with a Ti atom from the surface, which could indicate a reduction in the toxicity of the products. This study shows the relevance of water adsorption on the metal oxide surface for the stability and dissociation of the simulant DMMP and the nerve agents Sarin and Soman on TiO2.

Methane hydrates and contemporary climate change

USGS Publications Warehouse

Ruppel, Carolyn D.

2011-01-01

As the evidence for warming climate became better established in the latter part of the 20th century (IPCC 2001), some scientists raised the alarm that large quantities of methane (CH4) might be liberated by widespread destabilization of climate-sensitive gas hydrate deposits trapped in marine and permafrost-associated sediments (Bohannon 2008, Krey et al. 2009, Mascarelli 2009). Even if only a fraction of the liberated CH4 were to reach the atmosphere, the potency of CH4 as a greenhouse gas (GHG) and the persistence of its oxidative product (CO2) heightened concerns that gas hydrate dissociation could represent a slow tipping point (Archer et al. 2009) for Earth's contemporary period of climate change.

Shifts in oxidation states of cerium oxide nanoparticles detected inside intact hydrated cells and organelles

PubMed Central

Szymanski, Craig J.; Munusamy, Prabhakaran; Mihai, Cosmin; Xie, Yumei; Hu, Dehong; Gilles, Mary K.; Tyliszczak, Tolek; Thevuthasan, Suntharampillai; Baer, Donald R.; Orr, Galya

2015-01-01

Cerium oxide nanoparticles (CNPs) have been shown to induce diverse biological effects, ranging from toxic to beneficial. The beneficial effects have been attributed to the potential antioxidant activity of CNPs via certain redox reactions, depending on their oxidation state or Ce3+/Ce4+ ratio. However, this ratio is strongly dependent on the environment and age of the nanoparticles and it is unclear whether and how the complex intracellular environment impacts this ratio and the possible redox reactions of CNPs. To identify any changes in the oxidation state of CNPs in the intracellular environment and better understand their intracellular reactions, we directly quantified the oxidation states of CNPs outside and inside intact hydrated cells and organelles using correlated scanning transmission x-ray and super resolution fluorescence microscopies. By analyzing hundreds of small CNP aggregates, we detected a shift to a higher Ce3+/Ce4+ ratio in CNPs inside versus outside the cells, indicating a net reduction of CNPs in the intracellular environment. We further found a similar ratio in the cytoplasm and in the lysosomes, indicating that the net reduction occurs earlier in the internalization pathway. Together with oxidative stress and toxicity measurements, our observations identify a net reduction of CNPs in the intracellular environment, which is consistent with their involvement in potentially beneficial oxidation reactions, but also point to interactions that can negatively impact the health of cells. PMID:26056725

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.

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

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

Producing Durable Continuously Reinforced Concrete Pavement using Glass-ceramic Coated Reinforcing Steel

DTIC Science & Technology

2010-02-01

reinforcement if the enamel is broken  Embedded cement grains hydrate if enamel is cracked to self-heal with the formation of calcium silicate hydrate Goal...Reinforced Concrete Pavement The 600% volume change in the iron to iron oxide formation put the concrete in tension and it cracks an spalls BUILDING...corrodes prematurely and delaminates the pavement  Moisture and chlorides can move through the natural porosity of concrete and the cracks in the

Methane and other hydrocarbon gases in sediment from the southeastern North American continental margin

USGS Publications Warehouse

Kvenvolden, K.A.; Lorenson, T.D.

2000-01-01

Residual concentrations and distributions of hydrocarbon gases from methane to n-heptane were measured in sediments at seven sites on Ocean Drilling Program (ODP) Leg 164. Three sites were drilled at the Cape Fear Diapir of the Carolina Rise, and one site was drilled on the Blake Ridge Diapir. Methane concentrations at these sites result from microbial generation which is influenced by the amount of pore-water sulfate and possible methane oxidation. Methane hydrate was found at the Blake Ridge Diapir site. The other hydrocarbon gases at these sites are likely the produce of early microbial processes. Three sites were drilled on a transect of holes across the crest of the Blake Ridge. The base of the zone of gas-hydrate occurrence was penetrated at all three sites. Trends in hydrocarbon gas distributions suggest that methane is microbial in origin and that the hydrocarbon gas mixture is affected by diagenesis, outgassing, and, near the surface, by microbial oxidation. Methane hydrate was recovered at two of these three sites, although gas hydrate is likely present at all three sites. The method used here for determining amounts of residual hydrocarbon gases has its limitations and provides poor assessment of gas distributions, particularly in the stratigraphic interval below about ~ 100 mbsf. One advantage of the method, however, is that it yields sufficient quantities of gas for other studies such as isotopic determinations.

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.

NOTE: Measuring oxidative gelation of aqueous flour suspensions using the Rapid Visco Analyzer

USDA-ARS?s Scientific Manuscript database

The Rapid Visco Analyzer (RVA) was investigated as a tool to measure oxidative gelation capacity (OGC) of aqueous wheat-flour suspensions. One, club-wheat patent flour was used to determine optimal hydration time and 33 straight-grade flours (representing 12 hard and 31 soft varieties) were used to ...

Determining the flux of methane into Hudson Canyon at the edge of methane clathrate hydrate stability

USGS Publications Warehouse

Weinsten, A.; Navarrete, L; Ruppel, Carolyn D.; Weber, T.C.; Leonte, M.; Kellermann, M.; Arrington, E.; Valentine, D.L.; Scranton, M.L; Kessler, John D.

2016-01-01

Methane seeps were investigated in Hudson Canyon, the largest shelf-break canyon on the northern US Atlantic Margin. The seeps investigated are located at or updip of the nominal limit of methane clathrate hydrate stability. The acoustic identification of bubble streams was used to guide water column sampling in a 32 km2 region within the canyon's thalweg. By incorporating measurements of dissolved methane concentration with methane oxidation rates and current velocity into a steady-state box model, the total emission of methane to the water column in this region was estimated to be 12 kmol methane per day (range: 6 – 24 kmol methane per day). These analyses suggest this methane is largely retained inside the canyon walls below 300 m water depth, and that it is aerobically oxidized to near completion within the larger extent of Hudson Canyon. Based on estimated methane emissions and measured oxidation rates, the oxidation of this methane to dissolved CO2 is expected to have minimal influences on seawater pH. This article is protected by copyright. All rights reserved.

Determining the flux of methane into Hudson Canyon at the edge of methane clathrate hydrate stability

NASA Astrophysics Data System (ADS)

Weinstein, Alexander; Navarrete, Luis; Ruppel, Carolyn; Weber, Thomas C.; Leonte, Mihai; Kellermann, Matthias Y.; Arrington, Eleanor C.; Valentine, David L.; Scranton, Mary I.; Kessler, John D.

2016-10-01

Methane seeps were investigated in Hudson Canyon, the largest shelf-break canyon on the northern U.S. Atlantic Margin. The seeps investigated are located at or updip of the nominal limit of methane clathrate hydrate stability. The acoustic identification of bubble streams was used to guide water column sampling in a 32 km2 region within the canyon's thalweg. By incorporating measurements of dissolved methane concentration with methane oxidation rates and current velocity into a steady state box model, the total emission of methane to the water column in this region was estimated to be 12 kmol methane per day (range: 6-24 kmol methane per day). These analyses suggest that the emitted methane is largely retained inside the canyon walls below 300 m water depth, and that it is aerobically oxidized to near completion within the larger extent of Hudson Canyon. Based on estimated methane emissions and measured oxidation rates, the oxidation of this methane to dissolved CO2 is expected to have minimal influences on seawater pH.

Synthesis, characterization, solubility and stability studies of hydrate cocrystal of antitubercular Isoniazid with antioxidant and anti-bacterial Protocatechuic acid

NASA Astrophysics Data System (ADS)

Mashhadi, Syed Muddassir Ali; Yunus, Uzma; Bhatti, Moazzam Hussain; Ahmed, Imtiaz; Tahir, Muhammad Nawaz

2016-08-01

Isoniazid is an important component used in "triple therapy" to combat tuberculosis. It has reduced Tabletting formulations stability. Anti-oxidants are obligatory to counter oxidative stress, pulmonary inflammation, and free radical burst from macrophages caused in tuberculosis and other diseases. In the present study a hydrate cocrystal of Isoniazid with anti-oxidant and anti-inflammatory and anti-bacterial Protocatechuic acid (3,4-dihydroxybenzoic acid) in 1:1 is reported. This Cocrystal may have improved tabletting stability and anti-oxidant properties. Cocrystal structure analysis confirmed the existence of pyridine-carboxylic acid synthon in the Cocrystal. Other synthons of different graph sets involving Nsbnd H···O and Osbnd H···N bonds are formed between hydrazide group of isoniazid and coformer. Solubility studies revealed that cocrystal is less soluble as compared to isoniazid in buffer at pH 7.4 at 22 °C while stability studies at 80 °C for 24 h period disclosed the fact that cocrystal has higher stability than that of isoniazid.

Anaerobic methane oxidation in low-organic content methane seep sediments

USGS Publications Warehouse

Pohlman, John W.; Riedel, Michael; Bauer, James E.; Canuel, Elizabeth A.; Paull, Charles K.; Lapham, Laura; Grabowski, Kenneth S.; Coffin, Richard B.; Spence, George D.

2013-01-01

Sulfate-dependent anaerobic oxidation of methane (AOM) is the key sedimentary microbial process limiting methane emissions from marine sediments and methane seeps. In this study, we investigate how the presence of low-organic content sediment influences the capacity and efficiency of AOM at Bullseye vent, a gas hydrate-bearing cold seep offshore of Vancouver Island, Canada. The upper 8 m of sediment contains 14C. A fossil origin for the DIC precludes remineralization of non-fossil OM present within the sulfate zone as a significant contributor to pore water DIC, suggesting that nearly all sulfate is available for anaerobic oxidation of fossil seep methane. Methane flux from the SMT to the sediment water interface in a diffusion-dominated flux region of Bullseye vent was, on average, 96% less than at an OM-rich seep in the Gulf of Mexico with a similar methane flux regime. Evidence for enhanced methane oxidation capacity within OM-poor sediments has implications for assessing how climate-sensitive reservoirs of sedimentary methane (e.g., gas hydrate) will respond to ocean warming, particularly along glacially-influenced mid and high latitude continental margins.

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.

Role of hydration and water coordination in micellization of Pluronic block copolymers.

PubMed

Šturcová, Adriana; Schmidt, Pavel; Dybal, Jiří

2010-12-15

Raman, attenuated total reflectance FTIR, near-infrared spectroscopy, and DFT calculations have been used in a study of aqueous solutions of three tri-block copolymers poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) or PEO-PPO-PEO with commercial names Pluronic PE6200, PE6400 and F68. It is shown that the process of micellization as a response to increased temperature is reflected in the hydroxyl stretching region of infrared and Raman spectra, which contains information both about restructuring of water and changes of polymer chains in polymer/water aggregates. Raman spectra exhibit differences between individual Pluronics even at temperatures below the critical micellization temperature (CMT). According to the attenuated total reflection (ATR) FTIR spectra, the same five water coordination types defined by the number of donated/accepted hydrogen bonds are present in interacting water as in bulk water. It indicates that models considering mixed states of water with different hydrogen bonding environments provide appropriate descriptions of bound water both below and above the CMT. Above the CMT, aggregate hydration increases in the order PE6400 < PE6200 < F68, although that does not fully correspond to the EO/PO ratio, and points to the differences in microstructure of aggregates formed by each copolymer. This study relates nanoscale phenomena (hydrophobic and hydrophilic hydration) with the mesoscale phenomenon of micellization. Copyright © 2010 Elsevier Inc. All rights reserved.

Rapid rates of aerobic methane oxidation at the feather edge of gas hydrate stability in the waters of Hudson Canyon, US Atlantic Margin

NASA Astrophysics Data System (ADS)

Leonte, Mihai; Kessler, John D.; Kellermann, Matthias Y.; Arrington, Eleanor C.; Valentine, David L.; Sylva, Sean P.

2017-05-01

Aerobic oxidation is an important methane sink in seawater overlying gas seeps. Recent surveys have identified active methane seeps in the waters of Hudson Canyon, US Atlantic Margin near the updip limit of methane clathrate hydrate stability. The close proximity of these seeps to the upper stability limit of methane hydrates suggests that changing bottom water temperatures may influence the release rate of methane into the overlying water column. In order to assess the significance of aerobic methane oxidation in limiting the atmospheric expression of methane released from Hudson Canyon, the total extent of methane oxidized along with integrated oxidation rates were quantified. These calculations were performed by combining the measurements of the natural levels of methane concentrations, stable carbon isotopes, and water current velocities into kinetic isotope models yielding rates ranging from 22.8 ± 17 to 116 ± 76 nM/day with an average of 62.7 ± 37 nM/day. Furthermore, an average of 63% of methane released into the water column from an average depth of 515 m was oxidized before leaving this relatively small study area (6.5 km2). Results from the kinetic isotope model were compared to previously-published but concurrently-sampled ex situ measurements of oxidation potential performed using 13C-labeled methane. Ex situ rates were substantially lower, ranging from 0.1 to 22.5 nM/day with an average of 5.6 ± 2.3 nM/day, the discrepancy likely due to the inherent differences between these two techniques. Collectively, the results reveal exceptionally-rapid methane oxidation, with turnover times for methane as low as 0.3-3.7 days, indicating that methane released to the water column is removed quantitatively within the greater extent of Hudson Canyon. The red line represents the original Rayleigh model output, Eq. (1), detailed in the text. The red line represents the original Rayleigh model output, Eq. (1), detailed in the text.

Sulfur isotopic evidence for the origin of elemental sulfur in gas hydrate-bearing sediments of the northern South China Sea

NASA Astrophysics Data System (ADS)

Lin, Zhiyong; Sun, Xiaoming; Strauss, Harald; Lu, Yang; Xu, Li; Lu, Hongfeng; Teichert, Barbara M. A.; Peckmann, Jörn

2017-04-01

Elemental sulfur is a common intermediate in the sulfur cycle and contributes significantly to the fractionation of stable sulfur isotopes in different reservoirs in shelfal marine sediments (e.g., Canfield and Thamdrup, 1994). However, no study dedicated to the isotopic composition of elemental sulfur in seep environments has been conducted to the best of our knowledge, thus limiting further insight into the biochemical pathways involving elemental sulfur in such environments. In this study, elemental sulfur and pyrite were extracted from the sediment of a 200-m long gas hydrate-bearing core, which was obtained from the gas hydrate drilling expedition to the northern South China Sea in 2013 (Zhang et al., 2015). The sulfur isotopic composition of elemental sulfur was found to vary from -16 to +23 per mill, and pyrite yielded values ranging from -34 to +18 per mill. Interestingly, elemental sulfur revealed higher 34S contents (up to 30 per mill) than the associated pyrite in most sediment layers. Since elemental sulfur is only produced during oxidative pathways in the sulfur cycle, the studied elemental sulfur apparently represents the oxidation product of hydrogen sulfide by various electron acceptors such as Mn(IV) oxides or Fe(III) oxides (e.g., Thamdrup et al., 1993; Yao and Millero, 1996). Since there is little sulfur isotope fractionation for oxidative processes (Fry et al., 1986), the enrichment of elemental sulfur in 34S points to a pool of hydrogen sulfide depleted in 32S, which is best interpreted to result from sulfate-driven anaerobic oxidation of methane. References: Canfield D.E. and Thamdrup B. (1994) The production of 34S-depleted sulfide during bacterial disproportionation of elemental sulfur. Science 266, 1973. Fry B., Cox J., Gest H. and Hayer J.M. (1986) Discrimination between 34S and32S during bacterial metabolism of inorganic sulfur compounds. J. Bacteriol. 165, 328-330. Thamdrup B., Finster K., Hansen W. and Bak F. (1993) Bacterial disproportionation of elemental sulfur coupled to chemical reduction of iron and manganese. Appl. Env. Microbiol. 59, 101-108. Yao W. and Millero F.J. (1996) Oxidation of hydrogen sulfide by hydrous Fe(III) oxides in seawater. Mar. Chem. 52, 1-16. Zhang G., Liang J., Lu J.A., Yang S., Zhang M., Holland M., Schultheiss P., Su X., Sha Z., Xu H., Gong Y., Fu S., Wang L. and Kuang Z. (2015) Geological features, controlling factors and potential prospects of the gas hydrate occurrence in the east part of the Pearl River Mouth Basin, South China Sea. Mar. Pet. Geol. 67, 356-367.

Calorimetric determination of energetics of solid solutions of UO 2+ x with CaO and Y 2O 3

NASA Astrophysics Data System (ADS)

Mazeina, Lena; Navrotsky, Alexandra; Greenblatt, Martha

2008-02-01

Quantitative study of thermodynamic properties of solid solutions of UO 2+ x with divalent and trivalent oxides is important for predicting the behavior of oxide fuel. Although early literature work measured vapor pressure in some of these solid solutions, direct calorimetric measurements of enthalpies of formation have been hampered by the refractory nature of such oxides. First measurements of the enthalpies of formation in the systems UO 2+ x-CaO and UO 2+ x-YO 1.5, obtained by high-temperature oxide melt solution calorimetry, are reported. Both systems show significantly negative (exothermic) heats of formation from binary oxides (UO 2, plus O 2 and CaO or YO 1.5, as well as from UO 2 plus UO 3 and CaO or YO 1.5), consistent with reported free energy measurements in the urania-yttria system. The energetic contributions of oxygen content (oxidation of U 4+) and of charge balanced ionic substitution as well as defect clustering are discussed. Behavior of urania-yttria is compared to that of corresponding systems in which the tetravalent ion is Ce, Zr, or Hf. The substantial additional stability in the solid solutions compared to pure UO 2+ x may retard, in both thermodynamic and kinetic sense, the oxidation and leaching of spent fuel to form aqueous U 6+ and solid uranyl phases.

Photochromic, electrochromic, photoelectrochromic and photovoltaic devices

DOEpatents

Kostecki, Robert; McLarnon, Frank R.

2000-01-01

A light activated photoelectrochromic device is formed of a two-component system formed of a photoactive charge carrier generating material and electrochromic material (plus an elecrolyte). Light interacts with a semiconductive material to generate hole-electron charge carriers which cause a redox reaction in the electrochromic material. One device is formed of hydrated nickel oxide as the electrochromic layer and polycrystalline titanium dioxide as the charge generating material. The materials may be formed as discrete layers or mixed together. Because of the direct charge transfer between the layers, a circuit to apply a voltage to drive the electrochromic reaction is not required, although one can be used to enhance the reaction. The hydrated nickel oxide-titanium dioxide materials can also be used to form a photovoltaic device for generating electricity.

Composite anion-exchangers modified with nanoparticles of hydrated oxides of multivalent metals

NASA Astrophysics Data System (ADS)

Maltseva, T. V.; Kolomiets, E. O.; Dzyazko, Yu. S.; Scherbakov, S.

2018-02-01

Organic-inorganic composite ion-exchangers based on anion exchange resins have been obtained. Particles of one-component and two-component modifier were embedded using the approach, which allows us to realize purposeful control of a size of the embedded particles. The approach is based on Ostwald-Freundlich equation, which was adapted to deposition in ion exchange matrix. The equation was obtained experimentally. Hydrated oxides of zirconium and iron were applied to modification, concentration of the reagents were varied. The embedded particles accelerate sorption, the rate of which is fitted by the model equation of chemical reactions of pseudo-second order. When sorption of arsenate ions from very diluted solution (50 µg dm-3) occurs, the composites show higher distribution coefficients comparing with the pristine resin.

Amorphous cobalt potassium phosphate microclusters as efficient photoelectrochemical water oxidation catalyst

NASA Astrophysics Data System (ADS)

Zhang, Ye; Zhao, Chunsong; Dai, Xuezeng; Lin, Hong; Cui, Bai; Li, Jianbao

2013-12-01

A novel amorphous cobalt potassium phosphate hydrate compound (KCoPO4·H2O) is identified to be active photocatalyst for oxygen evolution reaction (OER) to facilitate hydrogen generation from water photolysis. It has been synthesized through a facile and cost-effective solution-based precipitation method using earth-abundant materials. Its highly porous structure and large surface areas are found to be responsible for the excellent electrochemical performance featuring a low OER onset at ∼550 mVSCE and high current density in alkaline condition. Unlike traditional cobalt-based spinel oxides (Co3O4, NiCo2O4) and phosphate (Co-Pi, Co(PO3)2) electrocatalysts, with proper energy band alignment for light-assisted water oxidation, cobalt potassium phosphate hydrate also exhibits robust visible-light response, generating a photocurrent density of ∼200 μA cm-2 at 0.7 VSCE. This catalyst could thus be considered as a promising candidate to perform photoelectrochemical water splitting.

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

One-step synthesis of hierarchically porous hybrid TiO2 hollow spheres with high photocatalytic activity

NASA Astrophysics Data System (ADS)

Liu, Ruiping; Ren, Feng; Yang, Jinlin; Su, Weiming; Sun, Zhiming; Zhang, Lei; Wang, Chang-an

2016-03-01

Hierarchically porous hybrid TiO2 hollow spheres were solvothermally synthesized successfully by using tetrabutyl titanate as titanium precursor and hydrated metal sulfates as soft templates. The as-prepared TiO2 spheres with hierarchically pore structures and high specific surface area and pore volume consisted of highly crystallized anatase TiO2 nanocrystals hybridized with a small amount of metal oxide from the hydrated sulfate. The proposed hydrated-sulfate assisted solvothermal (HAS) synthesis strategy was demonstrated to be widely applicable to various systems. Evaluation of the hybrid TiO2 hollow spheres for the photo-decomposition of methyl orange (MO) under visible-light irradiation revealed that they exhibited excellent photocatalytic activity and durability.

Structural characterization of terrestrial microbial Mn oxides from Pinal Creek, AZ

USGS Publications Warehouse

Bargar, J.R.; Fuller, C.C.; Marcus, M.A.; Brearley, A.J.; Perez De la Rosa, M.; Webb, S.M.; Caldwell, W.A.

2009-01-01

The microbial catalysis of Mn(II) oxidation is believed to be a dominant source of abundant sorption- and redox-active Mn oxides in marine, freshwater, and subsurface aquatic environments. In spite of their importance, environmental oxides of known biogenic origin have generally not been characterized in detail from a structural perspective. Hyporheic zone Mn oxide grain coatings at Pinal Creek, Arizona, a metals-contaminated stream, have been identified as being dominantly microbial in origin and are well studied from bulk chemistry and contaminant hydrology perspectives. This site thus presents an excellent opportunity to study the structures of terrestrial microbial Mn oxides in detail. XRD and EXAFS measurements performed in this study indicate that the hydrated Pinal Creek Mn oxide grain coatings are layer-type Mn oxides with dominantly hexagonal or pseudo-hexagonal layer symmetry. XRD and TEM measurements suggest the oxides to be nanoparticulate plates with average dimensions on the order of 11 nm thick ?? 35 nm diameter, but with individual particles exhibiting thickness as small as a single layer and sheets as wide as 500 nm. The hydrated oxides exhibit a 10-?? basal-plane spacing and turbostratic disorder. EXAFS analyses suggest the oxides contain layer Mn(IV) site vacancy defects, and layer Mn(III) is inferred to be present, as deduced from Jahn-Teller distortion of the local structure. The physical geometry and structural details of the coatings suggest formation within microbial biofilms. The biogenic Mn oxides are stable with respect to transformation into thermodynamically more stable phases over a time scale of at least 5 months. The nanoparticulate layered structural motif, also observed in pure culture laboratory studies, appears to be characteristic of biogenic Mn oxides and may explain the common occurrence of this mineral habit in soils and sediments. ?? 2008 Elsevier Ltd.

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

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.

Synthesis and X-ray Crystallography of [Mg(H2O)6][AnO2(C2H5COO)3]2 (An = U, Np, or Pu).

PubMed

Serezhkin, Viktor N; Grigoriev, Mikhail S; Abdulmyanov, Aleksey R; Fedoseev, Aleksandr M; Savchenkov, Anton V; Serezhkina, Larisa B

2016-08-01

Synthesis and X-ray crystallography of single crystals of [Mg(H2O)6][AnO2(C2H5COO)3]2, where An = U (I), Np (II), or Pu (III), are reported. Compounds I-III are isostructural and crystallize in the trigonal crystal system. The structures of I-III are built of hydrated magnesium cations [Mg(H2O)6](2+) and mononuclear [AnO2(C2H5COO)3](-) complexes, which belong to the AB(01)3 crystallochemical group of uranyl complexes (A = AnO2(2+), B(01) = C2H5COO(-)). Peculiarities of intermolecular interactions in the structures of [Mg(H2O)6][UO2(L)3]2 complexes depending on the carboxylate ion L (acetate, propionate, or n-butyrate) are investigated using the method of molecular Voronoi-Dirichlet polyhedra. Actinide contraction in the series of U(VI)-Np(VI)-Pu(VI) in compounds I-III is reflected in a decrease in the mean An═O bond lengths and in the volume and sphericity degree of Voronoi-Dirichlet polyhedra of An atoms.

Shifts in oxidation states of cerium oxide nanoparticles detected inside intact hydrated cells and organelles

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

Szymanski, Craig J.; Munusamy, Prabhakaran; Mihai, Cosmin

2015-09-01

Cerium oxide nanoparticles (CNPs) have been shown to induce diverse biological effects, ranging from toxic to beneficial. The beneficial effects have been attributed to the potential antioxidant activity of CNPs via certain redox reactions, depending on their oxidation state or Ce3+/Ce4+ ratio. However, this ratio is strongly dependent on the environment and age of the nanoparticles and it is unclear whether and how the complex intracellular environment impacts this ratio and the possible redox reactions of CNPs. To identify any changes in the oxidation state of CNPs in the intracellular environment and better understand their intracellular reactions, we directly quantifiedmore » the oxidation states of CNPs outside and inside intact hydrated cells and organelles using correlated scanning transmission x-ray and super resolution fluorescence microscopies. By analyzing hundreds of small CNP aggregates, we detected a shift to a higher Ce3+/Ce4+ ratio in CNPs inside versus outside the cells, indicating a net reduction of CNPs in the intracellular environment. We further found a similar ratio in the cytoplasm and in the lysosomes, indicating that the net reduction occurs earlier in the internalization pathway. Together with oxidative stress and toxicity measurements, our observations identify a net reduction of CNPs in the intracellular environment, which is consistent with their involvement in potentially beneficial oxidation reactions, but also point to interactions that can negatively impact the health of cells.« less

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

NUCLEAR REACTOR

DOEpatents

Miller, H.I.; Smith, R.C.

1958-01-21

This patent relates to nuclear reactors of the type which use a liquid fuel, such as a solution of uranyl sulfate in ordinary water which acts as the moderator. The reactor is comprised of a spherical vessel having a diameter of about 12 inches substantially surrounded by a reflector of beryllium oxide. Conventionnl control rods and safety rods are operated in slots in the reflector outside the vessel to control the operation of the reactor. An additional means for increasing the safety factor of the reactor by raising the ratio of delayed neutrons to prompt neutrons, is provided and consists of a soluble sulfate salt of beryllium dissolved in the liquid fuel in the proper proportion to obtain the result desired.

Gas hydrate decomposition recorded by authigenic barite at pockmark sites of the northern Congo Fan

NASA Astrophysics Data System (ADS)

Kasten, Sabine; Nöthen, Kerstin; Hensen, Christian; Spieß, Volkhard; Blumenberg, Martin; Schneider, Ralph R.

2012-12-01

The geochemical cycling of barium was investigated in sediments of pockmarks of the northern Congo Fan, characterized by surface and subsurface gas hydrates, chemosynthetic fauna, and authigenic carbonates. Two gravity cores retrieved from the so-called Hydrate Hole and Worm Hole pockmarks were examined using high-resolution pore-water and solid-phase analyses. The results indicate that, although gas hydrates in the study area are stable with respect to pressure and temperature, they are and have been subject to dissolution due to methane-undersaturated pore waters. The process significantly driving dissolution is the anaerobic oxidation of methane (AOM) above the shallowest hydrate-bearing sediment layer. It is suggested that episodic seep events temporarily increase the upward flux of methane, and induce hydrate formation close to the sediment surface. AOM establishes at a sediment depth where the upward flux of methane from the uppermost hydrate layer counterbalances the downward flux of seawater sulfate. After seepage ceases, AOM continues to consume methane at the sulfate/methane transition (SMT) above the hydrates, thereby driving the progressive dissolution of the hydrates "from above". As a result the SMT migrates downward, leaving behind enrichments of authigenic barite and carbonates that typically precipitate at this biogeochemical reaction front. Calculation of the time needed to produce the observed solid-phase barium enrichments above the present-day depths of the SMT served to track the net downward migration of the SMT and to estimate the total time of hydrate dissolution in the recovered sediments. Methane fluxes were higher, and the SMT was located closer to the sediment surface in the past at both sites. Active seepage and hydrate formation are inferred to have occurred only a few thousands of years ago at the Hydrate Hole site. By contrast, AOM-driven hydrate dissolution as a consequence of an overall net decrease in upward methane flux seems to have persisted for a considerably longer time at the Worm Hole site, amounting to a few tens of thousands of years.

Rethinking the global carbon cycle with a large, dynamic and microbially mediated gas hydrate capacitor

NASA Astrophysics Data System (ADS)

Dickens, Gerald R.

2003-08-01

Prominent negative δ13C excursions characterize several past intervals of abrupt (<100 kyr) environmental change. These anomalies, best exemplified by the >2.5‰ drop across the Paleocene/Eocene thermal maximum (PETM) ca. 55.5 Ma, command our attention because they lack explanation with conventional models for global carbon cycling. Increasingly, Earth scientists have argued that they signify massive release of CH4 from marine gas hydrates, although typically without considering the underlying process or the ensuing ramifications of such an interpretation. At the most basic level, a large, dynamic 'gas hydrate capacitor' stores and releases 13C-depleted carbon at rates linked to external conditions such as deep ocean temperature. The capacitor contains three internal reservoirs: dissolved gas, gas hydrate, and free gas. Carbon enters and leaves these reservoirs through microbial decomposition of organic matter, anaerobic oxidation of CH4 in shallow sediment, and seafloor gas venting; carbon cycles between these reservoirs through several processes, including fluid flow, precipitation and dissolution of gas hydrate, and burial. Numerical simulations show that simple gas hydrate capacitors driven by inferred changes in bottom water warming during the PETM can generate a global δ13C excursion that mimics observations. The same modeling extended over longer time demonstrates that variable CH4 fluxes to and from gas hydrates can partly explain other δ13C excursions, rapid and slow, large and small, negative and positive. Although such modeling is rudimentary (because processes and variables in modern and ancient gas hydrate systems remain poorly constrained), acceptance of a vast, externally regulated gas hydrate capacitor forces us to rethink δ13C records and the operation of the global carbon cycle throughout time.

Characterization of Microbial Community Structure in Gulf of Mexico Gas Hydrates: Comparative Analysis of DNA- and RNA-Derived Clone Libraries

PubMed Central

Mills, Heath J.; Martinez, Robert J.; Story, Sandra; Sobecky, Patricia A.

2005-01-01

The characterization of microbial assemblages within solid gas hydrate, especially those that may be physiologically active under in situ hydrate conditions, is essential to gain a better understanding of the effects and contributions of microbial activities in Gulf of Mexico (GoM) hydrate ecosystems. In this study, the composition of the Bacteria and Archaea communities was determined by 16S rRNA phylogenetic analyses of clone libraries derived from RNA and DNA extracted from sediment-entrained hydrate (SEH) and interior hydrate (IH). The hydrate was recovered from an exposed mound located in the northern GoM continental slope with a hydrate chipper designed for use on the manned-submersible Johnson Sea Link (water depth, 550 m). Previous geochemical analyses indicated that there was increased metabolic activity in the SEH compared to the IH layer (B. N. Orcutt, A. Boetius, S. K. Lugo, I. R. Macdonald, V. A. Samarkin, and S. Joye, Chem. Geol. 205:239-251). Phylogenetic analysis of RNA- and DNA-derived clones indicated that there was greater diversity in the SEH libraries than in the IH libraries. A majority of the clones obtained from the metabolically active fraction of the microbial community were most closely related to putative sulfate-reducing bacteria and anaerobic methane-oxidizing archaea. Several novel bacterial and archaeal phylotypes for which there were no previously identified closely related cultured isolates were detected in the RNA- and DNA-derived clone libraries. This study was the first phylogenetic analysis of the metabolically active fraction of the microbial community extant in the distinct SEH and IH layers of GoM gas hydrate. PMID:15933026

Response of the oceanic methane hydrate inventory to future climate change (AR5 RCP 4.5 - 8.5)

NASA Astrophysics Data System (ADS)

Hunter, S. J.; Goldobin, D.; Haywood, A. M.; Ridgwell, A. J.; Rees, J.

2012-12-01

We present results from a study designed to look at the change in global methane hydrate volume in response to AR5 Representative Concentration Pathways (Fifth Assessment Report RCP). We use bottom water conditions derived from 12 climate models within the CMIP5 multi-model ensemble along with a series of linear sea-level models to define boundary conditions. We model the change in global hydrate stability zone volume and hydrate inventory from the pre-industrial era and forward model through the RCP scenarios (to 2100 and 2300) to 5 kyr into the future. We find that thermal effects (i.e. warming induced hydrate dissociation) are dominant even when accompanied by extreme rates of sea level rise (i.e. 15 and 20 mm yr-1). Over the coming century dissociation is focussed within the top 100 m of Arctic and Subarctic sediments, beneath < ˜500 m water depth. Assuming a simple model of hydrate fill fraction (with a nominal 1% average hydrate-fill fraction) estimated globally integrated hydrate dissociation rates at ˜2100 are 120, 140 and 180 Tg CH4 yr-1 for RCP 4.5, 6.0 and 8.5 and at year ˜2300 are 150 and 600 Tg CH4 yr-1 under ECP 4.5 and 8.5 respectively. Under the unmitigated business-as-usual scenario (RCP 8.5) globally-integrated CH4 fluxes from hydrate dissociation could exceed estimates of natural sea-floor levels by 2100. Subsequent oxidation of resulting CH4 within the water column would significantly reduce atmospheric release rates to between ˜0.7 and ˜1.4 Tg CH4 yr-1 at ˜2100.

Reactions of CH3SH and CH3SSCH3 with gas-phase hydrated radical anions (H2O)n(•-), CO2(•-)(H2O)n, and O2(•-)(H2O)n.

PubMed

Höckendorf, Robert F; Hao, Qiang; Sun, Zheng; Fox-Beyer, Brigitte S; Cao, Yali; Balaj, O Petru; Bondybey, Vladimir E; Siu, Chi-Kit; Beyer, Martin K

2012-04-19

The chemistry of (H(2)O)(n)(•-), CO(2)(•-)(H(2)O)(n), and O(2)(•-)(H(2)O)(n) with small sulfur-containing molecules was studied in the gas phase by Fourier transform ion cyclotron resonance mass spectrometry. With hydrated electrons and hydrated carbon dioxide radical anions, two reactions with relevance for biological radiation damage were observed, cleavage of the disulfide bond of CH(3)SSCH(3) and activation of the thiol group of CH(3)SH. No reactions were observed with CH(3)SCH(3). The hydrated superoxide radical anion, usually viewed as major source of oxidative stress, did not react with any of the compounds. Nanocalorimetry and quantum chemical calculations give a consistent picture of the reaction mechanism. The results indicate that the conversion of e(-) and CO(2)(•-) to O(2)(•-) deactivates highly reactive species and may actually reduce oxidative stress. For reactions of (H(2)O)(n)(•-) with CH(3)SH as well as CO(2)(•-)(H(2)O)(n) with CH(3)SSCH(3), the reaction products in the gas phase are different from those reported in the literature from pulse radiolysis studies. This observation is rationalized with the reduced cage effect in reactions of gas-phase clusters. © 2012 American Chemical Society

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)

COLUMBIC OXIDE ADSORPTION PROCESS FOR SEPARATING URANIUM AND PLUTONIUM IONS

DOEpatents

Beaton, R.H.

1959-07-14

A process is described for separating plutonium ions from a solution of neutron irradiated uranium in which columbic oxide is used as an adsorbert. According to the invention the plutonium ion is selectively adsorbed by Passing a solution containing the plutonium in a valence state not higher than 4 through a porous bed or column of granules of hydrated columbic oxide. The adsorbed plutonium is then desorbed by elution with 3 N nitric acid.

Copper Silicate Hydrate Hollow Spheres Constructed by Nanotubes Encapsulated in Reduced Graphene Oxide as Long-Life Lithium-Ion Battery Anode.

PubMed

Wei, Xiujuan; Tang, Chunjuan; Wang, Xuanpeng; Zhou, Liang; Wei, Qiulong; Yan, Mengyu; Sheng, Jinzhi; Hu, Ping; Wang, Bolun; Mai, Liqiang

2015-12-09

Hierarchical copper silicate hydrate hollow spheres-reduced graphene oxide (RGO) composite is successfully fabricated by a facile hydrothermal method using silica as in situ sacrificing template. The electrochemical performance of the composite as lithium-ion battery anode was studied for the first time. Benefiting from the synergistic effect of the hierarchical hollow structure and conductive RGO matrix, the composite exhibits excellent long-life performance and rate capability. A capacity of 890 mAh/g is achieved after 200 cycles at 200 mA/g and a capacity of 429 mAh/g is retained after 800 cycles at 1000 mA/g. The results indicate that the strategy of combining hierarchical hollow structures with conductive RGO holds the potential in addressing the volume expansion issue of high capacity anode materials.

The impact of N,N-dimethyldodecylamine N-oxide (DDAO) concentration on the crystallisation of sodium dodecyl sulfate (SDS) systems and the resulting changes to crystal structure, shape and the kinetics of crystal growth.

PubMed

Summerton, Emily; Hollamby, Martin J; Zimbitas, Georgina; Snow, Tim; Smith, Andrew J; Sommertune, Jens; Bettiol, Jeanluc; Jones, Christopher; Britton, Melanie M; Bakalis, Serafim

2018-05-19

At low temperatures stability issues arise in commercial detergent products when surfactant crystallisation occurs, a process which is not currently well-understood. An understanding of the phase transition can be obtained using a simple binary SDS (sodium dodecyl sulfate) + DDAO (N,N-dimethyldodecylamine N-oxide) aqueous system. It expected that the crystallisation temperature of an SDS system can be lowered with addition of DDAO, thus providing a route to improve detergent stability. Detergent systems are typically comprised of anionic surfactants, non-ionic surfactants and water. This study explores the crystallisation of a three component system consisting of sodium dodecyl sulfate (SDS), N,N-dimethyldodecylamine N-oxide (DDAO), and water using wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC) and confocal Raman microscopy. The presence of DDAO lowered the crystallisation temperature of a 20 wt% SDS system. For all aqueous mixtures of SDS + DDAO at low temperatures, SDS hydrated crystals, SDS.1/2H 2 O or SDS·H 2 O, formed. SDS hydrates comprising of layers of SDS separated by water layers. DDAO tended to reside in the vicinity of these SDS crystals. In the absence of DDAO an additional intermediary hydrate structure, SDS.1/8H 2 O, formed whereas for mixed SDS + DDAO systems no such structure was detected during crystallisation. Copyright © 2018. Published by Elsevier Inc.

Formation of magnesium silicate hydrate (M-S-H) cement pastes using sodium hexametaphosphate

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

Zhang, Tingting; Department of Materials, Centre for Advanced Structural Ceramics, Imperial College London, South Kensington Campus, London SW7 2AZ; Department of Civil and Environmental Engineering, Imperial College London, South Kensington Campus, London SW7 2AZ

2014-11-15

Magnesium silicate hydrate (M-S-H) gel is formed by the reaction of brucite with amorphous silica during sulphate attack in concrete and M-S-H is therefore regarded as having limited cementing properties. The aim of this work was to form M-S-H pastes, characterise the hydration reactions and assess the resulting properties. It is shown that M-S-H pastes can be prepared by reacting magnesium oxide (MgO) and silica fume (SF) at low water to solid ratio using sodium hexametaphosphate (NaHMP) as a dispersant. Characterisation of the hydration reactions by x-ray diffraction and thermogravimetric analysis shows that brucite and M-S-H gel are formed andmore » that for samples containing 60 wt.% SF and 40 wt.% MgO all of the brucites react with SF to form M-S-H gel. These M-S-H cement pastes were found to have compressive strengths in excess of 70 MPa.« less

Ambient water and visible-light irradiation drive changes in graphene morphology, structure, surface chemistry, aggregation, and toxicity.

PubMed

Hu, Xiangang; Zhou, Ming; Zhou, Qixing

2015-03-17

The environmental behaviors and risks associated with graphene have attracted considerable attention. However, the fundamental effects of ambient water and visible-light irradiation on the properties and toxicity of graphene remain unknown. This work revealed that hydration and irradiation result in the transformation of large-sheet graphene to long-ribbon graphene. The thickness of the treated graphene decreased, and oxides were formed through the generation of singlet oxygen. In addition, hydration and irradiation resulted in greater disorder in the graphene structure and in the expansion of the d-spacing of the structure due to the introduction of water molecules and modifications of the functional groups. Oxidative modifications with two-stage (fast and low) kinetics enhanced the number of negative surface charges on the graphene and enhanced graphene aggregation. The above property alterations reduced the nanotoxicity of graphene to algal cells by reducing the generation of reactive oxygen species, diminishing protein carbonylation and decreasing tail DNA. A comparative study using graphene oxide suggested that oxidative modifications could play an important role in inhibiting toxicological activity. This study provides a preliminary approach for understanding the environmental behaviors of graphene and avoids overestimating the risks of graphene in the natural environment.

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.

Characterization and assessment of a novel poly(ethylene oxide)/polyurethane composite hydrogel (Aquavene) as a ureteral stent biomaterial.

PubMed

Gorman, S P; Tunney, M M; Keane, P F; Van Bladel, K; Bley, B

1998-03-15

The effective long-term use of indwelling ureteral stents is often hindered by the formation of encrusting deposits which may cause obstruction and blockage of the stent. Development of improved ureteral stent biomaterials capable of preventing or reducing encrustation is therefore particularly desirable. In this study, the suitability as a ureteral stent biomaterial of Aquavene, a novel poly(ethylene oxide)/polyurethane composite hydrogel was compared with that of silicone and polyurethane, two materials widely employed in ureteral stent manufacture. Examination of Aquavene in dry and hydrated states by confocal laser scanning microscopy, scanning electron microscopy, and atomic force microscopy showed the presence of numerous channels within a cellular matrix structure. The channel size increased considerably to as much as 10 microm in diameter in the hydrated state. Aquavene provided superior resistance to encrustation and intraluminal blockage over a 24-week period in a simulated urine flow model. Unobstructed urine flow continued with Aquavene at 24 weeks, whereas silicone and polyurethane stents became blocked with encrustation at 8 and 10 weeks, respectively. Weight loss within Aquavene on the order of 9% (w/w) over the 24-week flow period indicates that extraction of the noncrosslinked poly(ethylene oxide) hydrogel may be responsible for the prevention of encrustation blockage of this biomaterial. In the dry state, Aquavene was significantly harder than either silicone or polyurethane, as shown by Young's modulus, and rapidly became soft on hydration. These additional properties of Aquavene would facilitate ease of stent insertion in the dry state past obstructions in the ureter and provide improved patient comfort on subsequent biomaterial hydration in situ. Aquavene is a promising candidate for use in the urinary tract, as it is probable that effective long-term urine drainage would be maintained in vivo. Further evaluation of this novel biomaterial is therefore warranted.

Decrease in fruit moisture content heralds and might launch the onset of ripening processes.

PubMed

Frenkel, Chaim; Hartman, Thomas G

2012-10-01

It is known that fruit ripening is a genetically programmed event but it is not entirely clear what metabolic cue(s) stimulate the onset of ripening, ethylene action notwithstanding. Here, we examined the conjecture that fruit ripening might be evoked by an autonomously induced decrease in tissue water status. We found decline in water content occurring at the onset of ripening in climacteric and nonclimacteric fruit, suggesting that this phenomenon might be universal. This decline in water content persisted throughout the ripening process in some fruit, whereas in others it reversed during the progression of the ripening process. Applied ethylene also induced a decrease in water content in potato (Solanum tuberosum) tubers. In ethylene-mutant tomato (Solanum lycopersicum) fruit (antisense to1-aminocyclopropane carboxylate synthase), cold-induced decline in water content stimulated onset of ripening processes apparently independently of ethylene action, suggesting cause-and-effect relationship between decreasing water content and onset of ripening. The decline in tissue water content, occurring naturally or induced by ethylene, was strongly correlated with a decrease in hydration (swelling) efficacy of cell wall preparations suggesting that hydration dynamics of cell walls might account for changes in tissue moisture content. Extent of cell wall swelling was, in turn, related to the degree of oxidative cross-linking of wall-bound phenolic acids, suggesting that oxidant-induced wall restructuring might mediate cell wall and, thus, fruit tissue hydration status. We propose that oxidant-induced cell wall remodeling and consequent wall dehydration might evoke stress signaling for the onset of ripening processes. This study suggests that decline in fruit water content is an early event in fruit ripening. This information may be used to gauge fruit maturity for appropriate harvest date and for processing. Control of fruit hydration state might be used to regulate the onset of fruit ripening. © 2012 Institute of Food Technologists®

Influence of electrolytes on the microenvironment of F127 triblock copolymer micelles: a solvation and rotational dynamics study of coumarin dyes.

PubMed

Kumbhakar, Manoj; Ganguly, Rajib

2007-04-19

Dynamic Stokes' shift and fluorescence anisotropy measurements of coumarin 153 (C153) and coumarin 151 (C151) as fluorescence probes have been carried out to understand the influence of electrolytes (NaCl and LiCl) on the hydration behavior of aqueous (ethylene oxide)100-(propylene oxide)70-(ethylene oxide)100 (EO100-PO70-EO100, F127) block copolymer micelles. A small blue shift in the fluorescence spectra of C153 has been observed in presence of electrolytes due to the dehydration of the oxyethylene chains in the PEO-PPO region, although fluorescence spectra of C151 remain unaltered. The close vicinity of bulk water for C151 probably negates the effect of dehydration in the PEO region. Fluorescence anisotropy measurements indicate a gradual increase in microviscosity with electrolyte concentrations. The partial collapse of copolymer blocks in the presence of electrolytes has been suggested as a reason for the increase in microviscosity along with the strong hydration of ions in the corona region. The interplay between the ion hydration and the mechanically trapped water content, and specific interaction of ions, such as complexation of Li+ ions with the copolymer block, is found to control solvation dynamics in the corona region. In addition to that, it has been established that Na+ ions reside deep into the corona region whereas Li+ ions prefer to reside closer to the surface. Owing to its higher lyotropicity, LiCl influences the corona hydration to a greater extent than NaCl and sets in micelle-micelle interaction above the 2 M LiCl concentration, as reflected in the saturation of solvation time constants. The formation of larger clusters of F127 micelles above 2 M LiCl has been confirmed by dynamic light scattering measurements; however, such cluster formation is not evident with NaCl.

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

Effects of CO2 adsorption on proton migration on a hydrated ZrO2 surface: an ab initio molecular dynamics study.

PubMed

Sato, Ryuhei; Shibuta, Yasushi; Shimojo, Fuyuki; Yamaguchi, Shu

2017-08-02

Hydration reactions on a carbonate-terminated cubic ZrO 2 (110) surface were analyzed using ab initio molecular dynamics (AIMD) simulations. After hydration reactions, carbonates were still present on the surface at 500 K. However, these carbonates are very weak conjugate bases and only act as steric hindrance in proton hopping processes between acidic chemisorbed H 2 O molecules (Zr-OH 2 ) and monodentate hydroxyl groups (Zr-OH - ). Similar to a carbonate-free hydrated surface, Zr-OH 2 , Zr-OH - , and polydentate hydroxyl groups ([double bond splayed left]OH + ) were observed, while the ratio of acidic Zr-OH 2 was significantly larger than that on the carbonate-free hydrated surface. A thermodynamic discussion and bond property analysis reveal that CO 2 adsorption significantly decreases the basicity of surface oxide ions ([double bond splayed left]O), whereas the acidity of Zr-OH 2 is not affected. As a result, protons released from [double bond splayed left]OH + react with Zr-OH - to form Zr-OH 2 , leading to a deficiency of proton acceptor sites, which decreases the proton conductivity by the hopping mechanism.

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.

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.

Separation of rare earths from transition metals by liquid-liquid extraction from a molten salt hydrate to an ionic liquid phase.

PubMed

Rout, Alok; Binnemans, Koen

2014-02-28

The solvent extraction of trivalent rare-earth ions and their separation from divalent transition metal ions using molten salt hydrates as the feed phase and an undiluted fluorine-free ionic liquid as the extracting phase were investigated in detail. The extractant was tricaprylmethylammonium nitrate, [A336][NO3], and the hydrated melt was calcium nitrate tetrahydrate, Ca(NO3)2·4H2O. The extraction behavior of rare-earth ions was studied for solutions of individual elements, as well as for mixtures of rare earths in the hydrated melt. The influence of different extraction parameters was investigated: the initial metal loading in the feed phase, percentage of water in the feed solution, equilibration time, and the type of hydrated melt. The extraction of rare earths from Ca(NO3)2·4H2O was compared with extraction from CaCl2·4H2O by [A336][Cl] (Aliquat 336). The nitrate system was found to be the better one. The extraction and separation of rare earths from the transition metals nickel, cobalt and zinc were also investigated. Remarkably high separation factors of rare-earth ions over transition metal ions were observed for extraction from Ca(NO3)2·4H2O by the [A336][NO3] extracting phase. Furthermore, rare-earth ions could be separated efficiently from transition metal ions, even in melts with very high concentrations of transition metal ions. Rare-earth oxides could be directly dissolved in the Ca(NO3)2·4H2O phase in the presence of small amounts of Al(NO3)3·9H2O or concentrated nitric acid. The efficiency of extraction after dissolving the rare-earth oxides in the hydrated nitrate melt was identical to extraction from solutions with rare-earth nitrates dissolved in the molten phase. The stripping of the rare-earth ions from the loaded ionic liquid phase and the reuse of the recycled ionic liquid were also investigated in detail.

Fragmentation and hydration of tektites and microtektites

USGS Publications Warehouse

Glass, B.P.; Muenow, D.W.; Bohor, B.F.; Meeker, G.P.

1997-01-01

An examination of data collected over the last 30 years indicates that the percent of glass fragments vs. whole splash forms in the Cenozoic microtektite strewn fields increases towards the source crater (or source region). We propose that this is due to thermal stress produced when tektites and larger microtektites fall into water near the source crater while still relatively hot (>1150 ??C). We also find evidence (low major oxide totals, frothing when melted) for hydration of most of the North American tektite fragments and microtektites found in marine sediments. High-temperature mass spectrometry indicates that these tektite fragments and microtektites contain up to 3.8 wt% H2O. The H2O-release behavior during the high-temperature mass-spectrometric analysis, plus high Cl abundances (???0.05 wt%), indicate that the North. American tektite fragments and microtektites were hydrated in the marine environment (i.e., the H2O was not trapped solely on quenching from a melt). The younger Ivory Coast and Australasian microtektites do not exhibit much evidence of hydration (at least not in excess of 0.5 wt% H2O); this suggests that the degree of hydration increases with age. In addition, we find that some glass spherules (with 65 wt% SiO2 can undergo simple hydration in the marine environment, while impact glasses (with <65 wt% SiO2) can also undergo palagonitization.

Dissolution of Used Nuclear Fuel Using a TBP/N-Paraffin Solvent

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

Rudisill, T. S.; Shehee, T. C.; Jones, D. H.

2017-10-02

The dissolution of unirradiated used nuclear fuel (UNF) pellets pretreated for tritium removal was demonstrated using a tributly phosphate (TBP) solvent. Dissolution of pretreated fuel in TBP could potentially combine dissolution with two cycle of solvent extraction required for separating the actinides and lanthanides from other fission products. Dissolutions were performed using UNF surrogates prepared from both uranyl nitrate and uranium trioxide produced from the pretreatment process by adding selected actinide and stable fission product elements. In laboratory-scale experiments, the U dissolution efficiency ranged from 80-99+% for both the nitrate and oxide surrogate fuels. On average, 80% of the Pumore » and 50% of the Np and Am in the nitrate surrogate dissolved; however, little of the transuranic elements dissolved in the oxide form. The majority of the 3+ lanthanide elements dissolved. Only small amounts of Sr (0-1.6%) and Mo (0.1-1.7%) and essentially no Cs, Ru, Zr, or Pd dissolved.« less

Ionic conductors for solid oxide fuel cells

DOEpatents

Krumpelt, Michael; Bloom, Ira D.; Pullockaran, Jose D.; Myles, Kevin M.

1993-01-01

An electrolyte that operates at temperatures ranging from 600.degree. C. to 800.degree. C. is provided. The electrolyte conducts charge ionically as well as electronically. The ionic conductors include molecular framework structures having planes or channels large enough to transport oxides or hydrated protons and having net-positive or net-negative charges. Representative molecular framework structures include substituted aluminum phosphates, orthosilicates, silicoaluminates, cordierites, apatites, sodalites, and hollandites.

Thermodynamics of Manganese Oxides at Bulk and Nanoscale: Phase Formation, Transformation, Oxidation-Reduction, and Hydration

NASA Astrophysics Data System (ADS)

Birkner, Nancy R.

Natural manganese oxides are generally formed in surficial environments that are near ambient temperature and water-rich, and may be exposed to wet-dry cycles and a variety of adsorbate species that influence dramatically their level of hydration. Manganese oxide minerals are often poorly crystalline, nanophase, and hydrous. In the near-surface environment they are involved in processes that are important to life, such as water column oxygen cycling, biomineralization, and transport of minerals/nutrients through soils and water. These processes, often involving transformations among manganese oxide polymorphs, are governed by a complex interplay between thermodynamics and kinetics. Manganese oxides are also used in technology as catalysts, and for other applications. The major goal of this dissertation is to examine the energetics of bulk and nanophase manganese oxide phases as a function of particle size, composition, and surface hydration. Careful synthesis and characterization of manganese oxide phases with different surface areas provided samples for the study of enthalpies of formation by high temperature oxide melt solution calorimetry and of the energetics of water adsorption on their surfaces. These data provide a quantitative picture of phase stability and how it changes at the nanoscale. The surface energy of the hydrous surface of Mn3O4 is 0.96 +/- 0.08 J/m2, of Mn2O3 is 1.29 +/- 0.10 J/m2, and of MnO2 is 1.64 +/- 0.10 J/m2. The surface energy of the anhydrous surface of Mn3O4 is 1.62 +/- 0.08 J/m 2, of Mn2O3 is 1.77 +/- 0.10 J/m 2, and of MnO2 is 2.05 +/- 0.10 J/m2. Supporting preliminary findings (Navrotsky et al., 2010), the spinel phase (Mn3O4) has a lower surface energy (more stabilizing) than bixbyite, while the latter has a smaller surface energy than pyrolusite. These differences significantly change the positions in oxygen fugacity---temperature space of the redox couples Mn3O4-Mn2O 3 and Mn2O3-MnO2 favoring the lower surface enthalpy phase (the spinel Mn3O4) for smaller particle size and in the presence of surface hydration. Chemisorption of water onto anhydrous nanophase Mn2O 3 surfaces promotes rapidly reversible redox phase changes at room temperature as confirmed by calorimetry, X-ray diffraction, and titration for manganese average oxidation state. Water adsorption microcalorimetry (in situ) at room temperature measured the strongly exothermic integral enthalpy of water adsorption (-103.5 kJ/mol) and monitored the energetics of the redox phase transformation. Hydration-driven redox transformation of anhydrous nanophase Mn(III) 2O3, (high surface enthalpy of anhydrous surfaces 1.77 +/- 0.10 J/m2) to Mn(II,III)3O4 (lower surface enthalpy 0.96 +/- 0.08 J/m2) occurred during the first few doses of water vapor. Surface reduction of nanoparticle bixbyite (Mn 2O3) to hausmannite (Mn3O4) occurs under conditions where no such reactions are seen or expected on grounds of bulk thermodynamics in coarse-grained materials. Layered structure manganese oxides contain alkali or alkaline earth cations and water, are generally fine-grained, and have considerable thermodynamic stability. The surface enthalpies (SE) of layered and tunnel structure complex manganese oxides are significantly lower than those of the binary manganese oxide phases. The SE for hydrous surfaces and overall manganese average oxidation state (AOS) (value in parentheses) are: cryptomelane 0.77 +/- 0.10 J/m 2 (3.78), sodium birnessite 0.69 +/- 0.13 J/m2 (3.56), potassium birnessite 0.55 +/- 0.11 J/m2 (3.52), and calcium birnessite 0.41 +/- 0.11 J/m2 (3.50). Surface enthalpies of hydrous surfaces of the calcium manganese oxide nanosheets are: deltaCa 0.39MnO2.3nH2O 0.75 +/- 0.10 J/m2 (3.89) and deltaCa0.43MnO2.3nH2O 0.57 +/- 0.12 J/m2 (3.68). The surface enthalpy of the complex manganese oxides appears to decrease with decreasing manganese average oxidation state, that is, with greater mixed valence manganese (Mn 3+/4+). Low surface energy suggests loose binding of H2O on the internal and external surfaces and may be critical to catalysis in both natural and technological settings.

Capturing Transient Endoperoxide in the Singlet Oxygen Oxidation of Guanine.

PubMed

Lu, Wenchao; Liu, Jianbo

2016-02-24

The chemistry of singlet O2 toward the guanine base of DNA is highly relevant to DNA lesion, mutation, cell death, and pathological conditions. This oxidative damage is initiated by the formation of a transient endoperoxide through the Diels-Alder cycloaddition of singlet O2 to the guanine imidazole ring. However, no endoperoxide formation was directly detected in native guanine or guanosine, even at -100 °C. Herein, gas-phase ion-molecule scattering mass spectrometry was utilized to capture unstable endoperoxides in the collisions of hydrated guanine ions (protonated or deprotonated) with singlet O2 at ambient temperature. Corroborated by results from potential energy surface exploration, kinetic modeling, and dynamics simulations, various aspects of endoperoxide formation and transformation (including its dependence on guanine ionization and hydration states, as well as on collision energy) were determined. This work has pieced together reaction mechanisms, kinetics, and dynamics data concerning the early stage of singlet O2 induced guanine oxidation, which is missing from conventional condensed-phase studies. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

STABILIZED RARE EARTH OXIDES FOR A CONTROL ROD AND METHOD OF PREPARATION

DOEpatents

McNees, R.A.; Potter, R.A.

1964-01-14

A method is given for preparing mixed oxides of the formula MR/sub x/O/ sub 12/ wherein M is tungsten or molybdenum and R is a rare earth in the group consisting of samarium, europium, dysprosium, and gadolinium and x is 4 to 5. Oxides of this formula, and particularly the europiumcontaining species, are useful as control rod material for water-cooled nuclear reactors owing to their stability, favorable nuclear properties, and resistance to hydration. These oxides may be utilized as a dispersion in a stainlesssteel matrix. Preparation of these oxides is effected by blending tungsten oxide or molybdenum oxide with a rare earth oxide, compressing the mixture, and firing at an elevated temperature in an oxygen-containing atmosphere. (AEC)

Increasing the proton conductivity of sulfonated polyether ether ketone by incorporating graphene oxide: Morphology effect on proton dynamics

NASA Astrophysics Data System (ADS)

Leong, Jun Xing; Diño, Wilson Agerico; Ahmad, Azizan; Daud, Wan Ramli Wan; Kasai, Hideaki

2018-03-01

We synthesized graphene oxide-sulfonated polyether ether ketone (GO-SPEEK) composite membrane and compare its proton conductivity with that of Nafion® 117 and SPEEK membranes. From experimental measurements, we found that GO-SPEEK has better proton conductivity (σGO-SPEEK = 3.8 × 10-2 S cm-1) when compared to Nafion® 117 (σNafion = 2.4 × 10-2 S cm-1) and SPEEK (σSPEEK = 2.9 × 10-3 S cm-1). From density functional theory (DFT-) based total energy calculations, we found that GO-SPEEK has the shortest proton diffusion distance among the three membranes, yielding the highest tunneling probability. Hence, GO-SPEEK exhibits the highest conductivity. The short proton diffusion distance in GO-SPEEK, as compared to Nafion® 117 and SPEEK, can be attributed to the presence of oxygenated functional groups of GO in the polymer matrix. This also explains why GO-SPEEK requires the lowest hydration level to reach its maximum conductivity. Moreover, we have successfully shown that the proton conductivity σ is related to the tunneling probability T, i.e., σ = σ‧ exp(-1/T). We conclude that the proton diffusion distance and hydration level are the two most significant factors that determine the membrane’s good conductivity. The distance between ionic sites of the membrane should be small to obtain good conductivity. With this short distance, lower hydration level is required. Thus, a membrane with short separation between the ionic sites can have enhanced conductivity, even at low hydration conditions.

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.

Ion composition in a noctilucent cloud

NASA Technical Reports Server (NTRS)

Goldberg, R. A.; Witt, G.

1976-01-01

Ion composition at mesospheric altitudes was measured and compared between high and mid-latitude sites under summer daytime conditions. Rocket-borne measurements were made with pumped quadrupole ion mass spectrometers. The mid-latitude data were obtained at Wallops Island, Virginia on June 30, 1973, at 1510 LMT. Large quantities of hydronium cluster ions were observed through 109+, with maximum concentrations at 55+ and 73+. Also, cluster ions of nitric oxide were observed through 84+. The high latitude launch occurred at Kiruna, Sweden on August 2, 1973, at 0700 LMT following visual sighting of a noctilucent cloud on the prior evening. The data near mesopause shows cluster ions, but also a preponderance of heavy ions between 90 and 145 AMU, with groupings 18 AMU apart but unrelated to the more typical cluster ions. One possible set of consistent identifications leads to iron and iron oxide hydrates. These results may suggest the presence of metallic particulates and ions which form hydrated clusters ions.

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

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

Improvement of the cloud point extraction of uranyl ions by the addition of ionic liquids.

PubMed

Gao, Song; Sun, Taoxiang; Chen, Qingde; Shen, Xinghai

2013-12-15

The cloud point extraction (CPE) of uranyl ions by different kinds of extractants in Triton X-114 (TX-114) micellar solution was investigated upon the addition of ionic liquids (ILs) with various anions, i.e., bromide (Br(-)), tetrafluoroborate (BF4(-)), hexafluorophosphate (PF6(-)) and bis[(trifluoromethyl)sulfonyl]imide (NTf2(-)). A significant increase of the extraction efficiency was found on the addition of NTf2(-) based ILs when using neutral extractant tri-octylphosphine oxide (TOPO), and the extraction efficiency kept high at both nearly neutral and high acidity. However, the CPE with acidic extractants, e.g., bis(2-ethylhexyl) phosphoric acid (HDEHP) and 8-hydroxyquinoline (8-HQ) which are only effective at nearly neutral condition, was not improved by ILs. The results of zeta potential and (19)F NMR measurements indicated that the anion NTf2(-) penetrated into the TX-114 micelles and was enriched in the surfactant-rich phase during the CPE process. Meanwhile, NTf2(-) may act as a counterion in the CPE of UO2(2+) by TOPO. Furthermore, the addition of IL increased the separation factor of UO2(2+) and La(3+), which implied that in the micelle TOPO, NTf2(-) and NO3(-) established a soft template for UO2(2+). Therefore, the combination of CPE and IL provided a supramolecular recognition to concentrate UO2(2+) efficiently and selectively. Copyright © 2013 Elsevier B.V. All rights reserved.

5-hydroxymethylfurfural conversion by fungal aryl-alcohol oxidase and unspecific peroxygenase.

PubMed

Carro, Juan; Ferreira, Patricia; Rodríguez, Leonor; Prieto, Alicia; Serrano, Ana; Balcells, Beatriz; Ardá, Ana; Jiménez-Barbero, Jesús; Gutiérrez, Ana; Ullrich, René; Hofrichter, Martin; Martínez, Angel T

2015-08-01

Oxidative conversion of 5-hydroxymethylfurfural (HMF) is of biotechnological interest for the production of renewable (lignocellulose-based) platform chemicals, such as 2,5-furandicarboxylic acid (FDCA). To the best of our knowledge, the ability of fungal aryl-alcohol oxidase (AAO) to oxidize HMF is reported here for the first time, resulting in almost complete conversion into 2,5-formylfurancarboxylic acid (FFCA) in a few hours. The reaction starts with alcohol oxidation, yielding 2,5-diformylfuran (DFF), which is rapidly converted into FFCA by carbonyl oxidation, most probably without leaving the enzyme active site. This agrees with the similar catalytic efficiencies of the enzyme with respect to oxidization of HMF and DFF, and its very low activity on 2,5-hydroxymethylfurancarboxylic acid (which was not detected by GC-MS). However, AAO was found to be unable to directly oxidize the carbonyl group in FFCA, and only modest amounts of FDCA are formed from HMF (most probably by chemical oxidation of FFCA by the H2 O2 previously generated by AAO). As aldehyde oxidation by AAO proceeds via the corresponding geminal diols (aldehyde hydrates), the various carbonyl oxidation rates may be related to the low degree of hydration of FFCA compared with DFF. The conversion of HMF was completed by introducing a fungal unspecific heme peroxygenase that uses the H2 O2 generated by AAO to transform FFCA into FDCA, albeit more slowly than the previous AAO reactions. By adding this peroxygenase when FFCA production by AAO has been completed, transformation of HMF into FDCA may be achieved in a reaction cascade in which O2 is the only co-substrate required, and water is the only by-product formed. © 2014 The Authors. FEBS Journal published by John Wiley & Sons Ltd on behalf of FEBS.

On morphology of methane-derived authigenic carbonates

NASA Astrophysics Data System (ADS)

Logvina, E.; Matveeva, T.

2009-04-01

Studies of methane-derived carbonates revealed a great variety their morphological types. Although the processes of these carbonates formation is not clearly understood, it has been suggested that in general bacterially mediated processes of hydrocarbon oxidation, coupled with sulphate reduction, produce unusually high levels of alkalinity and dissolved inorganic carbon in the pore fluids that is partitioned between the precipitating carbonate and CO2 rich plumes which emanate into the water column (Aharon, 1994). These carbonates consist by three main CaCO3 polymorphs - calcite, aragonite and dolomite. Carbonates with different petrography cemented from these polymorphs can be classified according to their specific locality mode of formation and biogenic or non-biogenic origin (Greinert et al., 2002). There are classifications for the authigenic carbonates which are based on petrography, morphology, or based on age and origin. In this work we will consider the petrographical and morphological differences of authigenic carbonates. The large structures vary from 10 to 200 m size, named as chemoherm carbonates. Usually they cemented by pure aragonite with minor Mg-calcite admixture. These chemoherms rise up to 50 m above the seafloor. The structures are irregular in shape and have numerous pores and open pathways resulting from plumbing system of fluid expulsion. This type of authigenic carbonates was observed in the NE Black Sea (Michaelis et al., 2002), at the Hydrate Ridge area (Greinert et al., 2001), at Aleutian accretionary margin (Greinert et al., 2002). Diagenetic carbonates - carbonate cemented sediments both growing at the seafloor or within the sediment framework and showing a large variety of shapes (chimneys, crusts, concretions est.), with grey to dark-grey color. Petrographically the carbonate cement represents by Mg-calcite, protodolomite and dolomite. The diagenetic carbonates occur widely in the fluid venting areas. In particular, diagenetic carbonate chimneys were observed in the NE Atlantic, in the Gulf of Cadiz (Diaz del Rio et al., 2003), offshore Morocco (Magalhães et al., 2002), at northern Kattegat (Jensen et al., 1992), in the Pobitite Kamani area, in north-eastern Bulgaria (Botz et al., 1993). Clathrites (gas hydrate carbonates) are formed at the seawater/sediment interface or within the sediment in close contact with gas hydrates and bacterial mats. This type of the authigenic carbonates in direct contact with gas hydrates were identified and described by G. Bohrmann at Hydrate Ridge in 1998. According to (Bohrmann et al., 1998), they characterize by carbonate-cemented breccia composed of angular clasts cementing by Mg-calcite and aragonite. The brecciated structure causes by gas hydrate formation processes. A pure aragonite layers which form in elongated pores formerly occupied by gas hydrate are typical. This pseudomorphism resembles gas hydrate bubble structures. As a whole, clathrites are associated with bacterial mats on the seafloor next to gas hydrates and within the gas hydrate pore structure. References: G. Bohrmann, J. Greinert, E. Suess and M. Torres. Authigenic carbonates from the Cascadia subduction zone and their relation to gas hydrate stability: Geology, 1998, v. 26, pp. 647-650. J. Greinert, G. Bohrmann, and E. Suess. Gas hydrate-associated carbonates and methane-venting at Hydrate Ridge: Classification, distribution, and origin of authigenic lithologies, in Paull, C. and Dillon W.P. ed., Natural gas hydrates: Occurrence, distribution, and detection: Geophysical Monograph 124: 87-98, American Geophysical Union, 2001, pp. 99-113. J. Greinert, G. Bohrmann, and M. Elvert Stromatolitic fabric of authigenic carbonate crusts in 4850 m water depth, Aleutian accretionary margin: Result of anaerobic methane oxidation by Archaea at cold seeps. International Journal of Earth Sciences, 2002, 91, pp. 698-711. P. Aharon. Carbon and oxygen isotope tracers of submarine hydrocarbon emissions: Northern Gulf of Mexico. Israel Journal of earth Sciences, 1994, 43, pp. 157-164. P. Jensen, I. Aagaard, R. A. Burke Jr et al. "Bubbling reefs" in the Kattegat: submarine landscapes of carbonate-cemented rocks support a diverse ecosystem at methane seeps, Mar. Ecol. Prog. Ser., 1992, 83, pp. 103-112. R.W. Botz, V. Georgiev, P. Stoffers, et al. Stable isotope study of carbonate-cemented rocks from the Pobitite Kamani area, north-eastern Bulgaria. Geologische Rundschau, 1993, 82, pp. 663- 666. V. Diaz del Rio, L. Somoza, J. Martinez-Frias, et al. Vast field of hydrocarbon-derived carbonate chimneys related to the accretionary wedge/olistostrome of the Gulf of Cadiz. Marine Geology, 2003, 195, pp.177-200. V. Magalhães, C. Vasconcelos, L. Gaspar et al. Methane related aythigenic carbonates, chimneys and crusts from the Gulf of Cadiz, Geophysical Research Abstracts, 2002, Vol. 5, 12842. W. Michaelis, R. Seifert, K. Nauhaus, T. et al. Microbial Reefs in the Black Sea Fueled by Anaerobic Oxidation of Methane. Science, 2002, 297, pp. 1013-1015.

Synthesis of ion-exchange resin for selective thorium and uranyl ions sorption

NASA Astrophysics Data System (ADS)

Konovalov, Konstantin; Sachkov, Victor

2017-11-01

In this work, the method of ion-exchange resin synthesis selective to radionuclides (uranium and thorium) is presented. The method includes synthesis of polymeric styrene-divinylbenzene macroporous matrix with size of 0.1-0.2 mm, and its subsequent transformation by nitration and then reduction by tin (II) chloride. For passivation of active primary amines partially oxidation by oxygen from air is used. Obtained ion-exchange resin has ratio of sorption sum U+Th to sorption sum of other total rare-earth elements as 1:1.88 at ratio of solid to liquid phase 1:200. The proposed method of ion-exchange resin synthesis is scaled-up for laboratory reactors with volume of 5 and 50 liters.

Perchlorate-Coupled Carbon Monoxide (CO) Oxidation: Evidence for a Plausible Microbe-Mediated Reaction in Martian Brines.

PubMed

Myers, Marisa R; King, Gary M

2017-01-01

The presence of hydrated salts on Mars indicates that some regions of its surface might be habitable if suitable metabolizable substrates are available. However, several lines of evidence have shown that Mars' regolith contains only trace levels of the organic matter needed to support heterotrophic microbes. Due to the scarcity of organic carbon, carbon monoxide (CO) at a concentration of about 700 parts per million (about 0.4 Pa) might be the single most abundant readily available substrate that could support near-surface bacterial activity. Although a variety of electron acceptors can be coupled to CO oxidation, perchlorate is likely the most abundant potential oxidant in Mars' brines. Whether perchlorate, a potent chaotrope, can support microbial CO oxidation has not been previously documented. We report here the first evidence for perchlorate-coupled CO oxidation based on assays with two distinct euryarchaeal extreme halophiles. CO oxidation occurred readily in 3.8 M NaCl brines with perchlorate concentrations from 0.01 to 1 M. Both isolates were able to couple CO with perchlorate or chlorate under anaerobic conditions with or without nitrate as an inducer for nitrate reductase, which serves as a perchlorate reductase in extreme halophiles. In the presence of perchlorate, CO concentrations were reduced to levels well below those found in Mars' atmosphere. This indicates that CO could contribute to the survival of microbial populations in hydrated salt formations or brines if water activities are suitably permissive.

In situ Raman-based measurements of high dissolved methane concentrations in hydrate-rich ocean sediments

NASA Astrophysics Data System (ADS)

Zhang, Xin; Hester, Keith C.; Ussler, William; Walz, Peter M.; Peltzer, Edward T.; Brewer, Peter G.

2011-04-01

Ocean sediment dissolved CH4 concentrations are of interest for possible climate-driven venting from sea floor hydrate decomposition, for supporting the large-scale microbial anaerobic oxidation of CH4 that holds the oceanic CH4 budget in balance, and for environmental issues of the oil and gas industry. Analyses of CH4 from recovered cores near vent locations typically show a maximum of ˜1 mM, close to the 1 atmosphere equilibrium value. We show from novel in situ measurement with a Raman-based probe that geochemically coherent profiles of dissolved CH4 occur rising to 30 mM (pCH4 = 3 MPa) or an excess pressure ˜3× greater than CO2 in a bottle of champagne. Normalization of the CH4 Raman ν1 peak to the ubiquitous water ν2 bending peak provides a fundamental internal calibration. Very large losses of CH4 and fractions of other gases (CO2, H2S) must typically occur from recovered cores at gas rich sites. The new data are consistent with observations of microbial biomass and observed CH4 oxidation rates at hydrate rich sites and support estimates of a greatly expanded near surface oceanic pore water CH4 reservoir.

The role of "blebbing" in overcoming the hydrophobic barrier during biooxidation of elemental sulfur by Thiobacillus thiooxidans

USGS Publications Warehouse

Knickerbocker, C.; Nordstrom, D. Kirk; Southam, G.

2000-01-01

Brimstone Basin, in southeastern Yellowstone National Park, Wyoming is an ancient hydrothermal area containing solfataric alteration. Drainage waters flowing from Brimstone Basin had pH values as low as 1.23 and contained up to 1.7×106 MPN/ml acidophilic sulfur-oxidizing bacteria. Thiobacillus thiooxidans was the dominant sulfur-oxidizing bacterium recovered from an enrichment culture and was used in a structural examination of bacterial sulfur oxidation. Growth in these sulfur cultures occurred in two phases with cells in association with the macroscopic sulfur grains and in suspension above these grains. Colonization of sulfur grains by individual cells and microcolonies was facilitated by organic material that appeared to be responsible for bacterial adhesion. Transmission electron microscopy of negatively stained (2% [wt./vol.] uranyl acetate), sulfur-grown T. thiooxidans revealed extensive membrane blebbing (sloughing of outer membrane vesicles) and the presence of approximately 100 nm sized sulfur particles adsorbed to membrane material surrounding individual bacteria. Sulfite-grown bacteria did not possess membrane blebs. The amphipathic nature of these outer membrane vesicles appear to be responsible for overcoming the hydrophobic barrier necessary for the growth of T. thiooxidans on elemental sulfur.

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

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

The mechanism of vapor phase hydration of calcium oxide: implications for CO2 capture.

PubMed

Kudłacz, Krzysztof; Rodriguez-Navarro, Carlos

2014-10-21

Lime-based sorbents are used for fuel- and flue-gas capture, thereby representing an economic and effective way to reduce CO2 emissions. Their use involves cyclic carbonation/calcination which results in a significant conversion reduction with increasing number of cycles. To reactivate spent CaO, vapor phase hydration is typically performed. However, little is known about the ultimate mechanism of such a hydration process. Here, we show that the vapor phase hydration of CaO formed after calcination of calcite (CaCO3) single crystals is a pseudomorphic, topotactic process, which progresses via an intermediate disordered phase prior to the final formation of oriented Ca(OH)2 nanocrystals. The strong structural control during this solid-state phase transition implies that the microstructural features of the CaO parent phase predetermine the final structural and physicochemical (reactivity and attrition) features of the product hydroxide. The higher molar volume of the product can create an impervious shell around unreacted CaO, thereby limiting the efficiency of the reactivation process. However, in the case of compact, sintered CaO structures, volume expansion cannot be accommodated in the reduced pore volume, and stress generation leads to pervasive cracking. This favors complete hydration but also detrimental attrition. Implications of these results in carbon capture and storage (CCS) are discussed.

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.

Synthesis of nanocrystalline rare earth oxides by glycothermal method

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

Hosokawa, Saburo; Iwamoto, Shinji; Inoue, Masashi

2008-11-03

The reaction of yttrium acetate hydrate in 1,2-propanediol at 300 deg. C yielded a product containing acetate groups and glycol moieties. From this product, Y{sub 2}O{sub 3} was directly crystallized at 400 deg. C without the formation of a carbonate oxide phase. The thus-obtained Y{sub 2}O{sub 3} samples had a small crystallite size (2.2 nm) and significantly large surface area (280 m{sup 2}/g). Other nanocrystalline rare earth (Gd-Yb) oxides were also obtained by this method.

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.

Criticality experiments and analysis of molybdenum reflected cylindrical uranyl fluoride water solution reactors

NASA Technical Reports Server (NTRS)

Fieno, D.; Fox, T.; Mueller, R.

1972-01-01

Clean criticality data were obtained from molybdenum-reflected cylindrical uranyl-fluoride-water solution reactors. Using ENDF/B molybdenum cross sections, a nine energy group two-dimensional transport calculation of a reflected reactor configuration predicted criticality to within 7 cents of the experimental value. For these reactors, it was necessary to compute the reflector resonance integral by a detailed transport calculation at the core-reflector interface volume in the energy region of the two dominant resonances of natural molybdenum.

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.

Authigenic rhodochrosite from a gas hydrate-bearing structure in Lake Baikal

NASA Astrophysics Data System (ADS)

Krylov, Alexey A.; Hachikubo, Akihiro; Minami, Hirotsugu; Pogodaeva, Tatyana V.; Zemskaya, Tamara I.; Krzhizhanovskaya, Mariya G.; Poort, Jeffrey; Khlystov, Oleg M.

2018-02-01

Early diagenetic carbonates are rare in Lake Baikal. Siderite (Fe carbonate) concretions in the sediments were discovered only recently. Here, we discuss the first finding of rhodochrosite concretions (Mn carbonate) discovered in the near-bottom sediments of the gas hydrate-bearing seepage structure St. Petersburg-2 in the deep water environment of the Central Baikal Basin. The crystal lattice of rhodochrosite contains iron and calcium substituting to manganese. Based on pore water geochemistry and of δ 13C values of rhodochrosite (- 23.3 and - 29.4‰), carbon dioxide (+ 3.8 to - 16.1‰) and methane (- 63.2 to - 67.8‰), we show that carbonate crystallization most likely occurred during microbial anaerobic oxidation of organic matter, and that part of the oxygen making up the rhodochrosite seems to be derived from the 18O-rich water released from dissociating gas hydrates.

Studies on supercritical hydrothermal syntheses of uranium and lanthanide oxide particles and their reaction mechanisms

NASA Astrophysics Data System (ADS)

Hwang, DongKi; Tsukahara, Takehiko; Tanaka, Kosuke; Osaka, Masahiko; Ikeda, Yasuhisa

2015-11-01

In order to develop preparation method of raw metal oxide particles for low decontaminated MOX fuels by supercritical hydrothermal (SH) treatments, we have investigated behavior of aqueous solutions dissolving U(VI), Ln(III) (Ln: lanthanide = Ce, Pr, Nd, Sm, Tb), Cs(I), and Sr(II) nitrate or chloride compounds under SH conditions (temperature = 400-500 °C, pressure = 30-40 MPa). As a result, it was found that Ln(NO3)3 (Ln = Ce, Pr, Tb) compounds produce LnO2, that Ln(NO3)3 (Ln = Nd, Sm) compounds are hardly converted to their oxides, and that LnCl3 (Ln = Ce, Pr, Nd, Sm, Tb), CsNO3, and Sr(NO3)2 do not form their oxide compounds. Furthermore, HNO2 species were detected in the liquid phase obtained after treating HNO3 aqueous solutions containing Ln(NO3)3 (Ln = Ce, Pr, Tb) under SH conditions, and also NO2 and NO compounds were found to be produced by decomposition of HNO3. From these results, it was proposed that the Ln oxide (LnO2) particles are directly formed with oxidation of Ln(III) to Ln(IV) by HNO3 and HNO2 species in the SH systems. Moreover, the uranyl ions were found to form U3O8 and UO3 depending on the concentration of HNO3. From these results, it is expected that the raw metal oxide particles for low decontaminated MOX fuels are efficiently prepared by the SH method.

Beyond methane: Towards a theory for the Paleocene-Eocene Thermal Maximum

NASA Astrophysics Data System (ADS)

Higgins, John A.; Schrag, Daniel P.

2006-05-01

Extreme global warmth and an abrupt negative carbon isotope excursion during the Paleocene-Eocene Thermal Maximum (PETM) have been attributed to a massive release of methane hydrate from sediments on the continental slope [1]. However, the magnitude of the warming (5 to 6 °C [2],[3]) and rise in the depth of the CCD (> 2 km; [4]) indicate that the size of the carbon addition was larger than can be accounted for by the methane hydrate hypothesis. Additional carbon sources associated with methane hydrate release (e.g. pore-water venting and turbidite oxidation) are also insufficient. We find that the oxidation of at least 5000 Gt C of organic carbon is the most likely explanation for the observed geochemical and climatic changes during the PETM, for which there are several potential mechanisms. Production of thermogenic CH4 and CO2 during contact metamorphism associated with the intrusion of a large igneous province into organic rich sediments [5] is capable of supplying large amounts of carbon, but is inconsistent with the lack of extensive carbon loss in metamorphosed sediments, as well as the abrupt onset and termination of carbon release during the PETM. A global conflagration of Paleocene peatlands [6] highlights a large terrestrial carbon source, but massive carbon release by fire seems unlikely as it would require that all peatlands burn at once and then for only 10 to 30 ky. In addition, this hypothesis requires an order of magnitude increase in the amount of carbon stored in peat. The isolation of a large epicontinental seaway by tectonic uplift associated with volcanism or continental collision, followed by desiccation and bacterial respiration of the aerated organic matter is another potential mechanism for the rapid release of large amounts of CO2. In addition to the oxidation of the underlying marine sediments, the desiccation of a major epicontinental seaway would remove a large source of moisture for the continental interior, resulting in the desiccation and bacterial oxidation of adjacent terrestrial wetlands.

On the structure and dynamics of the hydrated sulfite ion in aqueous solution--an ab initio QMCF MD simulation and large angle X-ray scattering study.

PubMed

Eklund, Lars; Hofer, Thomas S; Pribil, Andreas B; Rode, Bernd M; Persson, Ingmar

2012-05-07

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) formalism has been applied in conjunction to experimental large angle X-ray scattering to study the structure and dynamics of the hydrated sulfite ion in aqueous solution. The results show that there is a considerable effect of the lone electron-pair on sulfur concerning structure and dynamics in comparison with the sulfate ion with higher oxidation number and symmetry of the hydration shell. The S-O bond distance in the hydrated sulfite ion has been determined to 1.53(1) Å by both methods. The hydrogen bonds between the three water molecules bound to each sulfite oxygen are only slightly stronger than those in bulk water. The sulfite ion can therefore be regarded as a weak structure maker. The water exchange rate is somewhat slower for the sulfite ion than for the sulfate ion, τ(0.5) = 3.2 and 2.6 ps, respectively. An even more striking observation in the angular radial distribution (ARD) functions is that the for sulfite ion the water exchange takes place in close vicinity of the lone electron-pair directed at its sides, while in principle no water exchange did take place of the water molecules hydrogen bound to sulfite oxygens during the simulation time. This is also confirmed when detailed pathway analysis is conducted. The simulation showed that the water molecules hydrogen bound to the sulfite oxygens can move inside the hydration shell to the area outside the lone electron-pair and there be exchanged. On the other hand, for the hydrated sulfate ion in aqueous solution one can clearly see from the ARD that the distribution of exchange events is symmetrical around the entire hydration sphere.

Uranium oxidation: Characterization of oxides formed by reaction with water by infrared and sorption analyses

NASA Astrophysics Data System (ADS)

Fuller, E. L.; Smyrl, N. R.; Condon, J. B.; Eager, M. H.

1984-04-01

Three different uranium oxide samples have been characterized with respect to the different preparation techniques. The results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. Inert gas sorption analyses and diffuse reflectance infrared studies combined with electron microscopy prove valuable in defining the chemistry and morphology of the oxidic products and hydrated intermediates.

Fluxes of dissolved methane from the seafloor at the landward limit of the gas hydrate stability zone offshore western Svalbard

NASA Astrophysics Data System (ADS)

Graves, Carolyn; Steinle, Lea; Niemann, Helge; Rehder, Gregor; Fisher, Rebecca; Lowry, Dave; Connelly, Doug; James, Rachael

2015-04-01

Seepage of methane from seafloor sediments offshore Svalbard may partly be driven by destabilization of gas hydrates as a result of bottom water warming. As the world's oceans are expected to continue to warm, in particular in the Arctic, destabilization of hydrate may become an important source of methane to ocean bottom waters and potentially to the overlying atmosphere where it contributes to further warming. In order to quantify the fate of methane from seafloor seeps, we have determined the distribution of dissolved methane in the water column on the upper slope and shelf offshore western Svalbard during three research cruises with RRS James Clark Ross (JR253) in 2011 and R/V Maria S. Merian (MSM21/4) and Heincke (HE387) in 2012. Combining discrete depth profile methane concentration data and surface seawater concentrations from an equilibrator-online system with oxidation rate measurements and atmospheric methane observations allows insight into the fate of methane input from the seafloor, and evaluation of the potential contributions of other methane sources. A simple box model considering oxidation and horizontal and vertical mixing indicates that the majority of seep methane is oxidized at depth. A plume of high methane concentrations is expected to persist more than 100 km downstream of the seepage area in the rapid barotropic West Spitsbergen Current, which flows northward towards the Arctic Ocean. We calculate that the diffusive sea-air flux of methane is largest on the shallow shelf, reaching 36 μmol m-2 day-1. Over the entire western Svalbard region there is a persistent, but small, source of methane from surface seawater to the overlying atmosphere. Measurements of the atmospheric methane carbon isotope signature indicate that the seafloor seeps do not make a significant contribution to atmospheric methane in this region, which is consistent with earlier studies. Observations downstream of the seepage region are necessary to further constrain potential for transport of previously hydrate-bound methane to the atmosphere, which would require a mechanism for enhanced vertical mixing of dissolved methane from bottom waters into the surface mixed layer.

Complex compound polyvinyl alcohol-titanic acid/titanium dioxide

NASA Astrophysics Data System (ADS)

Prosanov, I. Yu.

2013-02-01

A complex compound polyvinyl alcohol-titanic acid has been produced and investigated by means of IR and Raman spectroscopy, X-ray diffraction, and synchronous thermal analysis. It is claimed that it represents an interpolymeric complex of polyvinyl alcohol and hydrated titanium oxide.

75 FR 66433 - Mandatory Reporting of Greenhouse Gases

Federal Register 2010, 2011, 2012, 2013, 2014

2010-10-28

... oxygen process furnace shops. Lime Production 327410 Calcium oxide, calcium hydroxide, dolomitic hydrates... Chemists AOD argon-oxygen decarburization API American Petroleum Institute ASTM American Society for... Mandates Reform Act of 1995 VOD vacuum oxygen decarburization Table of Contents I. Background A. How is...

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).

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.

Proton Conduction in Grain-Boundary-Free Oxygen-Deficient BaFeO2.5+δ Thin Films

PubMed Central

Benes, Alexander; Molinari, Alan; Kruk, Robert; Brötz, Joachim; Chellali, Reda; Hahn, Horst

2017-01-01

Reduction of the operating temperature to an intermediate temperature range between 350 °C and 600 °C is a necessity for Solid Oxide Fuel/Electrolysis Cells (SOFC/SOECs). In this respect the application of proton-conducting oxides has become a broad area of research. Materials that can conduct protons and electrons at the same time, to be used as electrode catalysts on the air electrode, are especially rare. In this article we report on the proton conduction in expitaxially grown BaFeO2.5+δ (BFO) thin films deposited by pulsed laser deposition on Nb:SrTiO3 substrates. By using Electrochemical Impedance Spectroscopy (EIS) measurements under different wet and dry atmospheres, the bulk proton conductivity of BFO (between 200 °C and 300 °C) could be estimated for the first time (3.6 × 10−6 S cm−1 at 300 °C). The influence of oxidizing measurement atmosphere and hydration revealed a strong dependence of the conductivity, most notably at temperatures above 300 °C, which is in good agreement with the hydration behavior of BaFeO2.5 reported previously. PMID:29286321

Multiscale Molecular Dynamics Simulations of Model Hydrophobically Modified Ethylene Oxide Urethane Micelles.

PubMed

Yuan, Fang; Larson, Ronald G

2015-09-24

The flower-like micelles of various aggregation numbers of a model hydrophobically modified ethylene oxide urethane (HEUR) molecule, C16E45C16, and their corresponding starlike micelles, containing the surfactants C16E22 and C16E23, were studied by atomistic and coarse-grained molecular dynamic (MD) simulations. We used free energies from umbrella sampling to calculate the size distribution of micelle sizes and the average time for escape of a hydrophobic group from the micelle. Using the coarse-grained MARTINI force field, the most probable size of the model HEUR molecule was thereby determined to be about 80 hydrophobes per micelle and the average hydrophobe escape time to be about 0.1 s, both of which are consistent with previous experimental studies. Atomistic simulations reveal that hydrogen bond formation and the mean lifetime of hydration waters of the poly(ethylene oxide) (or PEO) groups are location-dependent in the HEUR micelle, with PEO groups immediately adjacent to the C16 groups forming the fewest hydrogen bonds with water and having hydration waters with longer lifetimes than those of the PEO groups located further away from the C16 groups.

Oral administration of Bifidobacterium breve attenuates UV-induced barrier perturbation and oxidative stress in hairless mice skin.

PubMed

Ishii, Yuki; Sugimoto, Saho; Izawa, Naoki; Sone, Toshiro; Chiba, Katsuyoshi; Miyazaki, Kouji

2014-07-01

Recent studies have shown that some probiotics affect not only the gut but also the skin. However, the effects of probiotics on ultraviolet (UV)-induced skin damage are poorly understood. In this study, we aim to examine whether oral administration of live Bifidobacterium breve strain Yakult (BBY), a typical probiotic, can attenuate skin barrier perturbation caused by UV and reactive oxygen species (ROS) in hairless mice. The mice were orally supplemented with a vehicle only or BBY once a day for nine successive days. Mouse dorsal skin was irradiated with UV from days 6 to 9. The day after the final irradiation, the transepidermal water loss (TEWL), stratum corneum hydration, and oxidation-related factors of the skin were evaluated. We elucidated that BBY prevented the UV-induced increase in TEWL and decrease in stratum corneum hydration. In addition, BBY significantly suppressed the UV-induced increase in hydrogen peroxide levels, oxidation of proteins and lipids, and xanthine oxidase activity in the skin. Conversely, antioxidant capacity did not change regardless of whether BBY was administered or not. In parameters we evaluated, there was a positive correlation between the increase in TEWL and the oxidation levels of proteins and lipids. Our results suggest that oral administration of BBY attenuates UV-induced barrier perturbation and oxidative stress of the skin, and this antioxidative effect is not attributed to enhancement of antioxidant capacity but to the prevention of ROS generation.

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

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.

Coupled interactions between volatile activity and Fe oxidation state during arc crustal processes

USGS Publications Warehouse

Humphreys, Madeleine C.S.; Brooker, R; Fraser, D.C.; Burgisser, A; Mangan, Margaret T.; McCammon, C

2015-01-01

Arc magmas erupted at the Earth’s surface are commonly more oxidized than those produced at mid-ocean ridges. Possible explanations for this high oxidation state are that the transfer of fluids during the subduction process results in direct oxidation of the sub-arc mantle wedge, or that oxidation is caused by the effect of later crustal processes, including protracted fractionation and degassing of volatile-rich magmas. This study sets out to investigate the effect of disequilibrium crustal processes that may involve coupled changes in H2O content and Fe oxidation state, by examining the degassing and hydration of sulphur-free rhyolites. We show that experimentally hydrated melts record strong increases in Fe3+/∑Fe with increasing H2O concentration as a result of changes in water activity. This is relevant for the passage of H2O-undersaturated melts from the deep crust towards shallow crustal storage regions, and raises the possibility that vertical variations in fO2 might develop within arc crust. Conversely, degassing experiments produce an increase in Fe3+/∑Fe with decreasing H2O concentration. In this case the oxidation is explained by loss of H2 as well as H2O into bubbles during decompression, consistent with thermodynamic modelling, and is relevant for magmas undergoing shallow degassing en route to the surface. We discuss these results in the context of the possible controls on fO2 during the generation, storage and ascent of magmas in arc settings, in particular considering the timescales of equilibration relative to observation as this affects the quality of the petrological record of magmatic fO2.

HALE STAIN FOR SIALIC ACID-CONTAINING MUCINS. ADAPTATION TO ELECTRON MICROSCOPY.

PubMed

GASIC, G; BERWICK, L

1963-10-01

The feasibility of using the Hale stain to identify cellular sialic acid-containing mucins by electron microscopy was investigated. Three kinds of mouse ascites tumor cells were fixed in neutral buffered formalin, exposed to fresh colloidal ferric oxide, treated with potassium ferrocyanide, imbedded in Selectron, and sectioned for electron microscopy. Additional staining with uranyl acetate and potassium permanganate was done after sectioning in order to increase contrast. Those cells known to be coated with sialomucin showed deposits of electron-opaque ferric ferrocyanide crystals in the areas where sialomucin concentrations were expected. When these cells were treated with neuraminidase beforehand, these deposits did not appear. It was concluded that, with the precautions and modifications described, the Hale stain can be successfully combined with electron microscopy to identify sialomucin.

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.

Interaction of water vapor with silicate glass surfaces: Mass-spectrometric investigations

NASA Astrophysics Data System (ADS)

Kudriavtsev, Yu.; Asomoza-Palacio, R.; Manzanilla-Naim, L.

2017-05-01

The secondary ion mass-spectroscopy technique was used to study the results of hydration of borosilicate, aluminosilicate, and soda-lime silicate glasses in 1H2 18O water vapor containing 97% of the isotope 18O. It is shown that hydration of the surface of the soda-lime silicate glass occurs as a result of the ion-exchange reaction with alkali metals. In the case of borosilicate and aluminosilicate glasses, water molecules decompose on the glass surface, with the observed formation of hydrogenated layer in the glass being the result of a solid-state chemical reaction—presumably, with the formation of hydroxides from aluminum and boron oxides.

21 CFR 310.545 - Drug products containing certain active ingredients offered over-the-counter (OTC) for certain uses.

Code of Federal Regulations, 2014 CFR

2014-04-01

... products. Aspirin Chloral hydrate Chlorobutanol Cyclomethycaine sulfate Eugenol Hexylresorcinol... isothiocyanate Aspirin Bismuth sodium tartrate Camphor (exceeding 3 percent) Capsaicin Capsicum Capsicum... oxide (vii) Poison ivy, poison oak, and poison sumac drug products. Alcohol Aspirin Benzethonium...

21 CFR 310.545 - Drug products containing certain active ingredients offered over-the-counter (OTC) for certain uses.

Code of Federal Regulations, 2013 CFR

2013-04-01

... products. Aspirin Chloral hydrate Chlorobutanol Cyclomethycaine sulfate Eugenol Hexylresorcinol... isothiocyanate Aspirin Bismuth sodium tartrate Camphor (exceeding 3 percent) Capsaicin Capsicum Capsicum... oxide (vii) Poison ivy, poison oak, and poison sumac drug products. Alcohol Aspirin Benzethonium...

21 CFR 310.545 - Drug products containing certain active ingredients offered over-the-counter (OTC) for certain uses.

Code of Federal Regulations, 2012 CFR

2012-04-01

... products. Aspirin Chloral hydrate Chlorobutanol Cyclomethycaine sulfate Eugenol Hexylresorcinol... isothiocyanate Aspirin Bismuth sodium tartrate Camphor (exceeding 3 percent) Capsaicin Capsicum Capsicum... oxide (vii) Poison ivy, poison oak, and poison sumac drug products. Alcohol Aspirin Benzethonium...

Retention and chemical speciation of uranium in an oxidized wetland sediment from the Savannah River Site.

PubMed

Li, Dien; Seaman, John C; Chang, Hyun-Shik; Jaffe, Peter R; Koster van Groos, Paul; Jiang, De-Tong; Chen, Ning; Lin, Jinru; Arthur, Zachary; Pan, Yuanming; Scheckel, Kirk G; Newville, Matthew; Lanzirotti, Antonio; Kaplan, Daniel I

2014-05-01

Uranium speciation and retention mechanisms onto Savannah River Site (SRS) wetland sediments was studied using batch (ad)sorption experiments, sequential extraction, U L3-edge X-ray absorption near-edge structure (XANES) spectroscopy, fluorescence mapping and μ-XANES. Under oxidized conditions, U was highly retained by the SRS wetland sediments. In contrast to other similar but much lower natural organic matter (NOM) sediments, significant sorption of U onto the SRS sediments was observed at pH < 4 and pH > 8. Sequential extraction indicated that the U species were primarily associated with the acid soluble fraction (weak acetic acid extractable) and organic fraction (Na-pyrophosphate extractable). Uranium L3-edge XANES spectra of the U-bound sediments were nearly identical to that of uranyl acetate. Based on fluorescence mapping, U and Fe distributions in the sediment were poorly correlated, U was distributed throughout the sample and did not appear as isolated U mineral phases. The primary oxidation state of U in these oxidized sediments was U(VI), and there was little evidence that the high sorptive capacity of the sediments could be ascribed to abiotic or biotic reduction to the less soluble U(IV) species or to secondary mineral formation. Collectively, this study suggests that U may be strongly bound to wetland sediments, not only under reducing conditions by reductive precipitation, but also under oxidizing conditions through NOM-uranium bonding. Published by Elsevier Ltd.

Conformation and hydration of surface grafted and free polyethylene oxide chains in solutions

NASA Astrophysics Data System (ADS)

Dahal, Udaya; Wang, Zilu; Dormidontova, Elena

Due to the wide application of polyethylene oxide (PEO), ranging from biomedicine to fuel cells, it is one of the most studied polymers in the scientific world. In order to elucidate detailed molecular-level insights on the impact of surface grafting on PEO conformation, we performed atomistic molecular dynamics simulations of PEO chains in solution and grafted to a flat gold surface in different solvents. We examined the hydration as well as conformation of the free chain compared to the grafted polymer in pure water and mixed solvents. We find that grafted chains are stiffer and have a stronger tendency to form helical structures in isobutyric acid or mixture of isobutyric acid and water solution than the free chains in corresponding solutions. For grafted chains exposed to pure water the random coil conformation is retained at low grafting density, but becomes stretched and more dehydrated as the grafting density or temperature increases. This research is supported by NSF (DMR-1410928).

Enhancement of the antimicrobial properties of orthorhombic molybdenum trioxide by thermal induced fracturing of the hydrates.

PubMed

Shafaei, Shahram; Van Opdenbosch, Daniel; Fey, Tobias; Koch, Marcus; Kraus, Tobias; Guggenbichler, Josef Peter; Zollfrank, Cordt

2016-01-01

The oxides of the transition metal molybdenum exhibit excellent antimicrobial properties. We present the preparation of molybdenum trioxide dihydrate (MoO3 × 2H2O) by an acidification method and demonstrate the thermal phase development and morphological evolution during and after calcination from 25 °C to 600 °C. The thermal dehydration of the material was found to proceed in two steps. Microbiological roll-on tests using Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa were performed and exceptional antimicrobial activities were determined for anhydrous samples with orthorhombic lattice symmetry and a large specific surface area. The increase in the specific surface area is due to crack formation and to the loss of the hydrate water after calcination at 300 °C. The results support the proposed antimicrobial mechanism for transition metal oxides, which based on a local acidity increase as a consequence of the augmented specific surface area. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of hydrogen intercalation on the critical parameters of YBa2Cu3O y

NASA Astrophysics Data System (ADS)

Bobylev, I. B.; Gerasimov, E. G.; Zyuzeva, N. A.; Terent'ev, P. B.

2017-10-01

The effect of hydrogenation at T = 150 and 200°C on the electrophysical properties of highly textured YBa2Cu3O y ceramics with different oxygen content has been investigated. Like hydration, hydrogenation results in the deterioration of these properties. However, in samples with high oxygen contents ( y = 6.96) hydrogenated at T = 150°C after oxidation (400°C) or recovery annealing with subsequent oxidation, the critical current density and first critical field increase compared to the initial state. The improvement of the properties occurs mainly in a magnetic field applied perpendicularly to the c axis. As after hydration, this is connected with the formation of planar defects in the course of low-temperature annealing. In addition, in the process of the hydrogenation, the partial reduction of copper occurs with the formation of microinclusions of Cu2O and other products of chemical decomposition, which are extra pinning centers of magnetic vortices.

Spectral reflectance properties (0.4-2.5 um) of secondary Fe-oxide, Fe-hydroxide, and Fe-sulfate-hydrate minerals associated with sulfide-bearing mine waste

USGS Publications Warehouse

Crowley, J.K.; Williams, D.E.; Hammarstrom1, J.M.; Piatak, N.; Mars, J.C.; Chou, I-Ming

2006-01-01

Fifteen Fe-oxide, Fe-hydroxide, and Fe-sulphate-hydrate mineral species commonly associated with sulphide bearing mine wastes were characterized by using X-ray powder diffraction and scanning electron microscope methods. Diffuse reflectance spectra of the samples show diagnostic absorption features related to electronic processes involving ferric and/or ferrous iron, and to vibrational processes involving water and hydroxyl ions. Such spectral features enable field and remote sensing based studies of the mineral distributions. Because secondary minerals are sensitive indicators of pH, Eh, relative humidity, and other environmental conditions, spectral mapping of these minerals promises to have important applications to mine waste remediation studies. This report releases digital (ascii) spectra (spectral_data_files.zip) of the fifteen mineral samples to facilitate usage of the data with spectral libraries and spectral analysis software. The spectral data are provided in a two-column format listing wavelength (in micrometers) and reflectance, respectively.

A model for the biological precipitation of Precambrian iron-formation

NASA Technical Reports Server (NTRS)

Laberge, G. L.

1986-01-01

A biological model for the precipitation of Precambrian iron formations is presented. Assuming an oxygen deficient atmosphere and water column to allow sufficient Fe solubility, it is proposed that local oxidizing environments, produced biologically, led to precipitation of iron formations. It is further suggested that spheroidal structures about 30 mm in diameter, which are widespread in low grade cherty rion formations, are relict forms of the organic walled microfossil Eosphaera tylerii. The presence of these structures suggests that the organism may have had a siliceous test, which allowed sufficient rigidity for accumulation and preservation. The model involves precipitation of ferric hydrates by oxidation of iron in the photic zone by a variety of photosynthetic organisms. Silica may have formed in the frustules of silica secreting organisms, including Eosphaera tylerii. Iron formates formed, therefore, by a sediment rain of biologically produced ferric hydrates and silica and other organic material. Siderite and hematite formed diagenetically on basin floors, and subsequent metamorphism produced magnetite and iron silicates.

Ice core measurements of 14CH4 show no evidence of methane release to atmosphere from methane hydrates during a large warming event 11,600 years ago

NASA Astrophysics Data System (ADS)

Petrenko, V. V.; Severinghaus, J. P.; Smith, A.; Riedel, K.; Brook, E.; Schaefer, H.; Baggenstos, D.; Harth, C. M.; Hua, Q.; Buizert, C.; Schilt, A.; Fain, X.; Mitchell, L.; Bauska, T. K.; Orsi, A. J.; Weiss, R. F.

2016-12-01

Marine methane hydrate destabilization has been proposed as a potentially large source of methane to the atmosphere in response to both past and future warming. We present new measurements of 14C of paleoatmospheric methane (CH4) over the Younger Dryas - Preboreal (YD - PB) abrupt warming event (≈11,600 years ago) from ancient ice outcropping at Taylor Glacier, Antarctica. The YD - PB abrupt warming was centered in the North Atlantic, occurred partway through the global warming of last deglaciation and was associated with a ≈ 50% increase in atmospheric CH4 concentrations. 14C can unambiguously identify CH4 emissions from "old carbon" sources, such as CH4 hydrates. All samples from before, during and after the abrupt warming and associated CH4 increase yielded 14CH4 values that are consistent with 14C of atmospheric CO2 at that time, indicating a purely contemporaneous methane source. Our results show that neither the abrupt regional warming nor the gradual global warming that preceded it resulted in detectable CH4 release to the atmosphere from CH4 hydrates during the YD - PB transition. Our results are thus consistent with the hypothesis that the vast majority of CH4 that is released from dissociating hydrates or other old-carbon seafloor CH4 sources is oxidized prior to reaching the atmosphere.

Uranium(VI) interactions with mackinawite in the presence and absence of bicarbonate and oxygen.

PubMed

Gallegos, Tanya J; Fuller, Christopher C; Webb, Samuel M; Betterton, William

2013-07-02

Mackinawite, Fe(II)S, samples loaded with uranium (10(-5), 10(-4), and 10(-3) mol U/g FeS) at pH 5, 7, and 9, were characterized using X-ray absorption spectroscopy and X-ray diffraction to determine the effects of pH, bicarbonate, and oxidation on uptake. Under anoxic conditions, a 5 g/L suspension of mackinawite lowered 5 × 10(-5) M uranium(VI) to below 30 ppb (1.26 × 10(-7) M) U. Between 82 and 88% of the uranium removed from solution by mackinawite was U(IV) and was nearly completely reduced to U(IV) when 0.012 M bicarbonate was added. Near-neighbor coordination consisting of uranium-oxygen and uranium-uranium distances indicates the formation of uraninite in the presence and absence of bicarbonate, suggesting reductive precipitation as the dominant removal mechanism. Following equilibration in air, mackinawite was oxidized to mainly goethite and sulfur and about 76% of U(IV) was reoxidized to U(VI) with coordination of uranium to axial and equatorial oxygen, similar to uranyl. Additionally, uranium-iron distances, typical of coprecipitation of uranium with iron oxides, and uranium-sulfur distances indicating bidentate coordination of U(VI) to sulfate were evident. The affinity of mackinawite and its oxidation products for U(VI) provides impetus for further study of mackinawite as a potential reactive medium for remediation of uranium-contaminated water.

Uranium(VI) interactions with mackinawite in the presence and absence of bicarbonate and oxygen

USGS Publications Warehouse

Gallegos, Tanya J.; Fuller, Christopher C.; Webb, Samuel M.; Betterton, William J.

2013-01-01

Mackinawite, Fe(II)S, samples loaded with uranium (10-5, 10-4, and 10-3 mol U/g FeS) at pH 5, 7, and 9, were characterized using X-ray absorption spectroscopy and X-ray diffraction to determine the effects of pH, bicarbonate, and oxidation on uptake. Under anoxic conditions, a 5 g/L suspension of mackinawite lowered 5 × 10-5 M uranium(VI) to below 30 ppb (1.26 × 10-7 M) U. Between 82 and 88% of the uranium removed from solution by mackinawite was U(IV) and was nearly completely reduced to U(IV) when 0.012 M bicarbonate was added. Near-neighbor coordination consisting of uranium–oxygen and uranium-uranium distances indicates the formation of uraninite in the presence and absence of bicarbonate, suggesting reductive precipitation as the dominant removal mechanism. Following equilibration in air, mackinawite was oxidized to mainly goethite and sulfur and about 76% of U(IV) was reoxidized to U(VI) with coordination of uranium to axial and equatorial oxygen, similar to uranyl. Additionally, uranium-iron distances, typical of coprecipitation of uranium with iron oxides, and uranium-sulfur distances indicating bidentate coordination of U(VI) to sulfate were evident. The affinity of mackinawite and its oxidation products for U(VI) provides impetus for further study of mackinawite as a potential reactive medium for remediation of uranium-contaminated water.

Orientation-dependent hydration structures at yttria-stabilized cubic zirconia surfaces

DOE PAGES

Hou, Binyang; Kim, Seunghyun; Kim, Taeho; ...

2016-11-30

Water interaction with surfaces is very important and plays key roles in many natural and technological processes. Because the experimental challenges that arise when studying the interaction water with specific crystalline surfaces, most studies on metal oxides have focused on powder samples, which averaged the interaction over different crystalline surfaces. As a result, studies on the crystal orientation-dependent interaction of water with metal oxides are rarely available in the literature. In this work, water adsorption at 8 mol % yttria-stabilized cubic single crystal zirconia (100) and (111) surfaces was studied in terms of interfacial hydration structures using high resolution X-raymore » reflectivity measurements. The interfacial electron density profiles derived from the structure factor analysis of the measured data show the existence of multiple layers of adsorbed water with additional peculiar metal adsorption near the oxide surfaces.Surface relaxation, depletion, and interaction between the adsorbed layers and bulk water are found to vary greatly between the two surfaces and are also different when compared to the previously studied (110) surface. The fractional ratio between chemisorbed and physisorbed water species were also quantitatively estimated, which turned out to vary dramatically from surface to surface. Finally, the result gives us a unique opportunity to reconsider the simplified 2:1 relation between chemisorption and physisorption, originally proposed by Morimoto et al. based on the adsorption isotherms of water on powder metal oxide samples.« less

The effect of actinoquinol with hyaluronic acid in eye drops on the optical properties and oxidative damage of the rabbit cornea irradiated with UVB rays.

PubMed

Čejka, Čestmír; Luyckx, Jacques; Ardan, Taras; Pláteník, Jan; Širc, Jakub; Michálek, Jiří; Čejková, Jitka

2010-01-01

Irradiation of the cornea with UVB rays leads to its oxidative damage, swelling and increased light absorption. We investigated changes in the corneal optics (evaluated by changes of corneal hydration and light absorption) and microscopical disturbances of corneas irradiated with UVB rays as influenced by eye drops containing actinoquinol with hyaluronic acid. Rabbit corneas were irradiated with a daily dose of 0.5 or 1.01 J cm(-2) of UVB rays (312 nm) for 4 days. During irradiation, the eye drops were applied on the right eye and buffered saline (or hyaluronic acid) on the left eye. On day 5 the rabbits were sacrificed and the corneas examined spectrophotometrically for light absorption. The corneal thickness (hydration) was measured using a pachymeter. Corneas of some other rabbits were examined immunohistochemically. After buffered saline treatment UVB rays evoked changes in the corneal optics and induced oxidative damage of the corneas. After actinoquinol-hyaluronic acid application, these changes were diminished. Hyaluronic acid alone was less effective. In conclusion, actinoquinol-hyaluronic acid eye drops decreased changes in corneal optics and suppressed oxidative damage in the UVB-irradiated cornea. However, the effective corneal protection by these eye drops was limited to the lower UVB dose. © 2010 The Authors. Journal Compilation. The American Society of Photobiology.

A controlled, three-part trial to investigate the barrier function and skin hydration properties of six skin protectants.

PubMed

Hoggarth, Andrew; Waring, Mike; Alexander, James; Greenwood, Amanada; Callaghan, Theresa

2005-12-01

In the treatment of incontinence dermatitis, a skin protectant primarily prevents skin breakdown due to moisture and biological irritants in urine and feces. To assess the barrier and skin hydration properties of six currently available skin protectants with different formulations, a controlled, three-phase study was conducted at a research facility in the UK among 18 healthy volunteers. The study addressed each product's efficacy against insult from a known irritant (sodium lauryl sulphate), skin hydration potential, and maintenance of skin barrier and barrier efficacy against maceration. Using white petrolatum (glycerin) as the positive control and untreated sites as the negative control, the results show that each one of the products tested has different performance properties. Products containing petrolatum demonstrated protection against irritants (P = 0.006 at 24 hours) and maceration (P < 0.005) and provided some skin hydration. Products containing dimethicone varied in protection against irritants (P < 0.005, or P > or = 0.806 at 24 hours) and have good skin hydration potential and low barrier efficacy (P > 0.500). Zinc oxide-based products showed protection against irritants (P < 0.005) but poor skin hydration and barrier properties to prevent maceration (P = 0.262). Overall, only the water-in-oil petrolatum- based product performed effectively within all the parameters tested. This study suggests that skin barrier protection involves more than the inclusion of an active barrier ingredient. Further testing and use of barrier products in the clinical setting will provide additional evidence for appropriate product selection.

Recovery of iron oxide from coal fly ash

DOEpatents

Dobbins, Michael S.; Murtha, Marlyn J.

1983-05-31

A high quality iron oxide concentrate, suitable as a feed for blast and electric reduction furnaces is recovered from pulverized coal fly ash. The magnetic portion of the fly ash is separated and treated with a hot strong alkali solution which dissolves most of the silica and alumina in the fly ash, leaving a solid residue and forming a precipitate which is an acid soluble salt of aluminosilicate hydrate. The residue and precipitate are then treated with a strong mineral acid to dissolve the precipitate leaving a solid residue containing at least 90 weight percent iron oxide.

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)

Geochemistry of vanadium in an epigenetic, sandstone-hosted vanadium- uranium deposit, Henry Basin, Utah

USGS Publications Warehouse

Wanty, R.B.; Goldhaber, M.B.; Northrop, H.R.

1990-01-01

The epigenetic Tony M vanadium-uranium orebody in south-central Utah is hosted in fluvial sandstones of the Morrison Formation (Upper Jurassic). Measurements of the relative amounts of V+3 and V +4 in ore minerals show that V+3 is more abundant. Thermodynamic calculations show that vanadium was more likely transported to the site of mineralization as V+4. The ore formed as V+4 was reduced by hydrogen sulfide, followed by hydrolysis and precipitation of V+3 in oxide minerals or chlorite. Uranium was transported as uranyl ion (U+6), or some complex thereof, and reduced by hydrogen sulfide, forming coffinite. Detrital organic matter in the rocks served as the carbon source for sulfate-reducing bacteria. Vanadium most likely was derived from the dissolution of iron-titanium oxides. Uranium probably was derived from the overlying Brushy Basin Member of the Morrison Formation. Previous studies have shown that the ore formed at the density-stratified interface between a basinal brine and dilute meteoric water. The mineralization processes described above occurred within the mixing zone between these two fluids. -from Authors

Adsorption of uranium(VI) to manganese oxides: X-ray absorption spectroscopy and surface complexation modeling.

PubMed

Wang, Zimeng; Lee, Sung-Woo; Catalano, Jeffrey G; Lezama-Pacheco, Juan S; Bargar, John R; Tebo, Bradley M; Giammar, Daniel E

2013-01-15

The mobility of hexavalent uranium in soil and groundwater is strongly governed by adsorption to mineral surfaces. As strong naturally occurring adsorbents, manganese oxides may significantly influence the fate and transport of uranium. Models for U(VI) adsorption over a broad range of chemical conditions can improve predictive capabilities for uranium transport in the subsurface. This study integrated batch experiments of U(VI) adsorption to synthetic and biogenic MnO(2), surface complexation modeling, ζ-potential analysis, and molecular-scale characterization of adsorbed U(VI) with extended X-ray absorption fine structure (EXAFS) spectroscopy. The surface complexation model included inner-sphere monodentate and bidentate surface complexes and a ternary uranyl-carbonato surface complex, which was consistent with the EXAFS analysis. The model could successfully simulate adsorption results over a broad range of pH and dissolved inorganic carbon concentrations. U(VI) adsorption to synthetic δ-MnO(2) appears to be stronger than to biogenic MnO(2), and the differences in adsorption affinity and capacity are not associated with any substantial difference in U(VI) coordination.

The structure of graphene oxide membranes in liquid water, ethanol and water-ethanol mixtures

NASA Astrophysics Data System (ADS)

Talyzin, Alexandr V.; Hausmaninger, Tomas; You, Shujie; Szabó, Tamás

2013-12-01

The structure of graphene oxide (GO) membranes was studied in situ in liquid solvents using synchrotron radiation X-ray diffraction in a broad temperature interval. GO membranes are hydrated by water similarly to precursor graphite oxide powders but intercalation of alcohols is strongly hindered, which explains why the GO membranes are permeated by water and not by ethanol. Insertion of ethanol into the membrane structure is limited to only one monolayer in the whole studied temperature range, in contrast to precursor graphite oxide powders, which are intercalated with up to two ethanol monolayers (Brodie) and four ethanol monolayers (Hummers). As a result, GO membranes demonstrate the absence of ``negative thermal expansion'' and phase transitions connected to insertion/de-insertion of alcohols upon temperature variations reported earlier for graphite oxide powders. Therefore, GO membranes are a distinct type of material with unique solvation properties compared to parent graphite oxides even if they are composed of the same graphene oxide flakes.The structure of graphene oxide (GO) membranes was studied in situ in liquid solvents using synchrotron radiation X-ray diffraction in a broad temperature interval. GO membranes are hydrated by water similarly to precursor graphite oxide powders but intercalation of alcohols is strongly hindered, which explains why the GO membranes are permeated by water and not by ethanol. Insertion of ethanol into the membrane structure is limited to only one monolayer in the whole studied temperature range, in contrast to precursor graphite oxide powders, which are intercalated with up to two ethanol monolayers (Brodie) and four ethanol monolayers (Hummers). As a result, GO membranes demonstrate the absence of ``negative thermal expansion'' and phase transitions connected to insertion/de-insertion of alcohols upon temperature variations reported earlier for graphite oxide powders. Therefore, GO membranes are a distinct type of material with unique solvation properties compared to parent graphite oxides even if they are composed of the same graphene oxide flakes. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr04631a

Nanoparticle-supported and magnetically recoverable palladium (Pd) catalyst: a selective and sustainable oxidation protocol with high turnover number

EPA Science Inventory

A magnetic nanoparticle-supported ruthenium hydroxide catalyst was readily prepared from inexpensive starting materials and shown to catalyze hydration of nitriles with excellent yield in benign aqueous medium. Catalyst recovery using an external magnetic field, superior activity...

Spectroscopic Properties of Neodymium and Erbium-Doped Magnesium Oxide Ceramics

DTIC Science & Technology

2015-09-01

may contribute to the difference between the measured and expected values (such as varied hydration levels in the starting materials), there has...believe that such impurities forms from the thermal decomposition of the organic binders and dispersants used in the processing. We believe the

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

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.

Method of increasing the sulfation capacity of alkaline earth sorbents

DOEpatents

Shearer, J.A.; Turner, C.B.; Johnson, I.

1980-03-13

A system and method for increasing the sulfation capacity of alkaline earth carbonates to scrub sulfur dioxide produced during the fluidized bed combustion of coal in which partially sulfated alkaline earth carbonates are hydrated in a fluidized bed to crack the sulfate coating and convert the alkaline earth oxide to the hydroxide. Subsequent dehydration of the sulfate-hydroxide to a sulfate-oxide particle produces particles having larger pore size, increased porosity, decreased grain size and additional sulfation capacity. A continuous process is disclosed.

Method of increasing the sulfation capacity of alkaline earth sorbents

DOEpatents

Shearer, John A.; Turner, Clarence B.; Johnson, Irving

1982-01-01

A system and method for increasing the sulfation capacity of alkaline earth carbonates to scrub sulfur dioxide produced during the fluidized bed combustion of coal in which partially sulfated alkaline earth carbonates are hydrated in a fluidized bed to crack the sulfate coating and convert the alkaline earth oxide to the hydroxide. Subsequent dehydration of the sulfate-hydroxide to a sulfate-oxide particle produces particles having larger pore size, increased porosity, decreased grain size and additional sulfation capacity. A continuous process is disclosed.

More Evidence of the Importance of Amorphous Silicates in CM Carbonaceous Chondrites: New Observations from a Fine-Grained Rim in the CM2 Chondrite, TIL 91722

NASA Astrophysics Data System (ADS)

Brearley, A. J.; Le Guillou, C.

2015-07-01

A fine-grained rim in TIL 91722 contains abundant amorphous silicate material containing nanophase sulfides. Phyllosilicates are rare. The amorphous material has a high ferric iron content indicative of oxidation coupled with hydration.

21 CFR 184.1428 - Magnesium hydroxide.

Code of Federal Regulations, 2011 CFR

2011-04-01

... salt or by hydration of reactive grades of magnesium oxide. (b) The ingredient meets the specifications... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Magnesium hydroxide. 184.1428 Section 184.1428... Listing of Specific Substances Affirmed as GRAS § 184.1428 Magnesium hydroxide. (a) Magnesium hydroxide...

21 CFR 184.1428 - Magnesium hydroxide.

Code of Federal Regulations, 2010 CFR

2010-04-01

... hydration of reactive grades of magnesium oxide. (b) The ingredient meets the specifications of the Food... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Magnesium hydroxide. 184.1428 Section 184.1428 Food... Specific Substances Affirmed as GRAS § 184.1428 Magnesium hydroxide. (a) Magnesium hydroxide (Mg(OH)2, CAS...

75 FR 62853 - Reno-Sparks Indian Colony Liquor Control Ordinance

Federal Register 2010, 2011, 2012, 2013, 2014

2010-10-13

... alcohol, hydrated oxide or ethyl, or spirit or wine, which is commonly produced by the fermentation or... ordinance. (iii) ``Beer'' shall mean any beverage obtained by the alcoholic fermentation of any infusion or.... (xix) ``Wine'' shall mean any alcoholic beverage obtained by fermentation of fruits (grapes, berries...

75 FR 44011 - Liquor Ordinance of the Wichita and Affiliated Tribes

Federal Register 2010, 2011, 2012, 2013, 2014

2010-07-27

... alcohol, hydrated oxide of ethyl, or spirit or wine which is commonly produced by the fermentation or..., including but not limited to beer or cereal malt beverages obtained by the alcoholic fermentation of an... any alcoholic beverage obtained by fermentation of fruits (grapes, berries, apples, etc.) or other...

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+).

Investigation of the structure and stability of SnO2 nanocrystal and its surface-bound water

NASA Astrophysics Data System (ADS)

Wang, H.; Wesolowski, D. J.; Proffen, T. E.; Kolesnikov, A. I.; Vlcek, L.; Wang, W.; Feygenson, M.; Sofo, J. O.; Anovitz, L.

2012-12-01

Driven partly by a myriad use of engineered metal oxide nanoparticles, understanding their stabilities and interactions with environmental matrix during and after applications are desired. SnO2 (cassiterite) is one of the frequently used oxides in solid-state gas sensors and oxidation catalysts. A close relationship between the gas sensitivity and catalysis of oxides with their surface chemistry ensures continuous interests in the study of SnO2-water interfacial complexity (unavoidable "contamination" in which water can potentially participate in reactions and change SnO2 conductivity). Such information is important, as the existence of hydration layers on the surface of SnO2 nanoparticles not only play a critical role in stabilizing the nanoparticle but also affect its selectivity/sensitivity, as a nanosensor. SnO2 nanoparticles (2-5 nm) synthesized by a wet chemical route are dominated by {110} faces and are capped with H2O or D2O water molecules (after purification), depending on isotopic composition of water used for syntheses. When water is in direct contact with terminal Sn and O atoms, there is a controversial argument as to whether or not dissociative adsorption occurs (i.e., formation of hydroxyl groups). Although theoretical studies point toward a tendency for dissociative configuration in the direct contact layer, experimental studies have not unambiguously confirmed this conclusion. We present combined investigations using neutron total scattering (NPDF at the NOMAD beamline, SNS) and inelastic neutron scattering (INS at the SEQUOIA beamline, SNS) techniques as static and dynamic probes to reveal structure and dynamics of water and SnO2 nanocrystalline stability upon dehydration. The NPDF results (measured with deuterated samples) suggest layered water configurations with G(r) signals dominated by O-D bonds at 0.98 Å, and the second hydration layer that gives a broad peak at 2.5-4 Å. There is no evidence of a third hydration layer at 5-7 Å as shown by our previous molecular dynamic (MD) simulations, perhaps because this outermost hydration layer is not laterally-ordered parallel to the oxide surface and thus contributes a much weaker G(r) signal than the first two layers. Additionally, due to the relatively broad distribution of D-D distances and Fourier termination ripples, NPDF results cannot provide unambiguous evidence about the formation of hydroxylated surfaces, even though the dissociative MD model gives a better fitted result. Upon heating to 250 °C (at 10-7 bar), SnO2 nanoparticles start to show surface transformation and increased crystallinity before completion of dehydration. This likely corresponds to the minimum concentration of surface-bound groups required to stabilize the nanoparticles (i.e., < 0.7 monolayer coverage). Attempts to remove D2O/OD- groups below this threshold lead to rapidly increase of crystallinity. INS experiments on SnO2 nanoparticles with a minimum threshold coverage and with those from a fully hydrated sample clearly suggested dissociated water configurations with no observations of H2O bending modes in the sample with a minimum threshold coverage. Corresponding ab initio MD simulation on SnO2 (110) surface for a comparison with INS results is underway to provide a complete picture of SnO2-water surface dynamics.

Tuning the Hydration and Lubrication of the Embedded Load-Bearing Hydrogel Fibers.

PubMed

Zhang, Ran; Feng, Yange; Ma, Shuanhong; Cai, Meirong; Yang, Jun; Yu, Bo; Zhou, Feng

2017-03-07

One of the most prominent properties of hydrogels is their excellent hydrolubrication that derives from the strong hydration of the gel network. However, excessive hydration makes hydrogels exhibit a very poor mechanical property, which limits their practical applications. Here, we prepared a novel composite surface of hydrogel nanofibers embedded in an anodic aluminum oxide substrate which exhibited both excellent lubrication and a high load-bearing capacity. Through the copolymerization of acrylic acid and 3-sulfopropyl methacrylate potassium salt, the gel network swelled sufficiently in aqueous solution and caused high osmotic pressure repulsion to bear heavy loads and hence exhibited excellent aqueous lubrication (μ ≈ 0.01). Notably, the friction coefficient of gels showed no dependence on the load in the experiment, whereas it was strongly influenced by the sliding velocity. Additionally, both electrolyte solution and ionic surfactants affect the conformation of the polymer chains, which results in a significant impact on the friction properties of hydrogel fibers.

Highly improved hydration level sensing properties of copper oxide films with sodium and potassium doping

NASA Astrophysics Data System (ADS)

Sahin, Bünyamin; Kaya, Tolga

2016-01-01

In this study, un-doped, Na-doped, and K-doped nanostructured CuO films were successfully synthesized by the successive ionic layer adsorption and reaction (SILAR) technique and then characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and current-voltage (I-V) measurements. Structural properties of the CuO films were affected from doping. The XRD pattern indicates the formation of polycrystalline CuO films with no secondary phases. Furthermore, doping affected the crystal structure of the samples. The optimum conductivity values for both Na and K were obtained at 4 M% doping concentrations. The comparative hydration level sensing properties of the un-doped, Na-doped, and K-doped CuO nanoparticles were also investigated. A significant enhancement in hydration level sensing properties was observed for both 4 M% Na and K-doped CuO films for all concentration levels. Detailed discussions were reported in the study regarding atomic radii, crystalline structure, and conductivity.

Characteristics of gas hydrate-bearing sediments of the northern South China Sea: insight into past hydrate episodic dissociations and intensities of seepage

NASA Astrophysics Data System (ADS)

Chen, F.; Su, X.; Zhou, Y.; Zhang, G.; Zhuang, C.; Lu, H.

2016-12-01

In 2013 the second China's major gas hydrate expedition, GMGS2, cored and recovered abundant gas hydrates at five sites, which were located in the South China Sea.Site GMGS08 (95m long) contained two gas hydrate intervals and five authigenic carbonate intervals. We analyzed carbon and oxygen isotopes of authigenic carbonates and foraminifera shells in sediments recovered at this site, in order to understanding of features of hydrate-bearing sediments and timing of gas hydrate dissociation and methane seepage at this site. An age of younger than 0.27 Ma was estimated for the 95 m sedimentary sequences at Site GMGS08. A detailed age model was further established by employing of U/Th and AMS14C dating of authigenic carbonates and seep bivalve fragments. These carbonates are featured by 13C-depleted (with a range from -38.9‰ to 56.7‰ δ13C) and positive δ18O (from 2.94‰ to 5.66‰ δ18O) values. A further analysis indicated the formation of carbonates were correlated to methane seepages derived from gas hydrate dissociation. Subsequently, these five authigenic carbonates intervals were seen as five hydrate episodic dissociation events since last 0.27Ma at this site. The most significant event during the period of 0.11 Ma to 0.13 Ma were account for the formation of thick authigenic carbonate (with the lowest -56.8‰ δ13C value) platform on paleo-seafloor at this site. The upmost authigenic carbonates interval is just overlying on the top of the upper gas hydrate occurrence zone, and it represents the latest methane seepage event with an age of 26ka to 36ka. Well correlated to these five events, it existed five intervals with strongly 13C-depleted carbon (-15.85‰ PDB) of foraminifera shells both from benthic and planktonic. The anomalous δ13C depletion records of planktonic G. ruber shells should be caused by formation of secondary authigenic carbonates on the shells, which were derived from the anaerobic oxidation of methane (AOM). The analyses on carbonate samples indicated varied intensity of methane flux in each event. The most intensive methane venting flux occurred during the event of 0.11 Ma to 0.13 Ma, which is correlated to a warm and relative high sea level period of MIS stage 5. These records obtained at Site GMGS08 implied much complicated causes for formation of authigenic carbonates and gas hydrate episodic dissociation.

Hydrogenation of liquid natural rubber via diimide reduction in hydrazine hydrate/hydrogen peroxide system

NASA Astrophysics Data System (ADS)

Yusof, Muhammad Jefri Mohd; Jamaluddin, Naharullah; Abdullah, Ibrahim; Yusoff, Siti Fairus M.

2015-09-01

Liquid natural rubber (LNR) with molecular weight of lower than 105 and shorter polymeric chain than natural rubber was prepared. LNR was then hydrogenated via diimide reduction by oxidation of hydrazine hydrate with hydrogen peroxide. The unsaturated units of the rubber were converted into saturated hydrocarbon to strengthen the backbone of the polymer so it was able to resist thermal degradation. The results indicated that hydrogenation degree of the product (HLNR) could be extended to 91.2% conversion under appropriate conditions. The hydrogenated LNR (HLNR) was characterized using Fourier-Transform Infrared (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopy. The physical characteristics of HLNR were analyzed with Termogravimetric Analysis (TGA).

Controllable cyanation of carbon-hydrogen bonds by zeolite crystals over manganese oxide catalyst

PubMed Central

Wang, Liang; Wang, Guoxiong; Zhang, Jian; Bian, Chaoqun; Meng, Xiangju; Xiao, Feng-Shou

2017-01-01

The synthesis of organic nitriles without using toxic cyanides is in great demand but challenging to make. Here we report an environmentally benign and cost-efficient synthesis of nitriles from the direct oxidative cyanation of primary carbon-hydrogen bonds with easily available molecular oxygen and urea. The key to this success is to design and synthesize manganese oxide catalysts fixed inside zeolite crystals, forming a manganese oxide catalyst with zeolite sheath (MnOx@S-1), which exhibits high selectivity for producing nitriles by efficiently facilitating the oxidative cyanation reaction and hindering the side hydration reaction. The work delineates a sustainable strategy for synthesizing nitriles while avoiding conventional toxic cyanide, which might open a new avenue for selective transformation of carbon-hydrogen bonds. PMID:28504259

Microstructural response of variably hydrated Ca-rich montmorillonite to supercritical CO2.

PubMed

Lee, Mal-Soon; McGrail, B Peter; Glezakou, Vassiliki-Alexandra

2014-01-01

First-principles molecular dynamics simulations were carried out to explore the mechanistic and thermodynamic ramifications of the exposure of variably hydrated Ca-rich montmorillonites to supercritical CO2 and CO2-SO2 mixtures under geologic storage conditions. In sub- to single-hydrated systems (≤ 1W), CO2 intercalation causes interlamellar expansion of 8-12%, while systems transitioning to 2W may undergo contraction (∼ 7%) or remain almost unchanged. When compared to ∼2W hydration state, structural analysis of the ≤ 1W systems, reveals more Ca-CO2 contacts and partial transition to vertically confined CO2 molecules. Infrared spectra and projected vibrational frequency analysis imply that intercalated Ca-bound CO2 are vibrationally constrained and contribute to the higher frequencies of the asymmetric stretch band. Reduced diffusion coefficients of intercalated H2O and CO2 (10(-6)-10(-7) cm(2)/s) indicate that Ca-montmorillonites in ∼ 1W hydration states can be more efficient in capturing CO2. Simulations including SO2 imply that ∼ 0.66 mmol SO2/g clay can be intercalated without other significant structural changes. SO2 is likely to divert H2O away from the cations, promoting Ca-CO2 interactions and CO2 capture by further reducing CO2 diffusion (10(-8) cm(2)/s). Vibrational bands at ∼ 1267 or 1155 cm(-1) may be used to identify the chemical state (oxidation states +4 or +6, respectively) and the fate of sulfur contaminants.

Communication: Fourier-transform infrared probing of remarkable quantities of gas trapped in cold homogeneously nucleated nanodroplets.

PubMed

Uras-Aytemiz, Nevin; Devlin, J Paul

2013-07-14

Studies of catalyzed all-vapor gas-hydrate formation on a sub-second timescale have been extended with a special focus on liquid-droplet compositions at the instant of hydrate crystallization. This focus has been enabled by inclusion of methanol in the all-vapor mixture. This slows droplet to gas-hydrate conversion near 200 K to a time scale suited for standard FTIR sampling. Such droplet data are sought as a guide to ongoing efforts to reduce the amount of guest catalyst required for instant formation of the gas hydrates. For the same reason, all-vapor sampling has also been extended to the generation of long-lived liquid droplets with reduced or no water content. Observations of single-solvent droplets show that surprising quantities of gas molecules are trapped during rapid droplet growth. For example, CO2 is trapped at levels near 50 mol. % in droplets of acetone, tetrahydrofuran, or trimethylene oxide formed under CO2 pressures of several Torr in a cold-chamber at 170 K. Less but significant amounts of gas are trapped at higher temperatures, or in methanol or water-methanol droplets. The droplet metastability appears to commonly lead to formation of bubbles larger than the original nanodroplets. Besides serving as a guide for the all-vapor gas-hydrate studies, the semiquantitative evidence of extensive trapping of gases is expected to have a role in future studies of atmospheric aerosols.

Communication: Fourier-transform infrared probing of remarkable quantities of gas trapped in cold homogeneously nucleated nanodroplets

NASA Astrophysics Data System (ADS)

Uras-Aytemiz, Nevin; Devlin, J. Paul

2013-07-01

Studies of catalyzed all-vapor gas-hydrate formation on a sub-second timescale have been extended with a special focus on liquid-droplet compositions at the instant of hydrate crystallization. This focus has been enabled by inclusion of methanol in the all-vapor mixture. This slows droplet to gas-hydrate conversion near 200 K to a time scale suited for standard FTIR sampling. Such droplet data are sought as a guide to ongoing efforts to reduce the amount of guest catalyst required for instant formation of the gas hydrates. For the same reason, all-vapor sampling has also been extended to the generation of long-lived liquid droplets with reduced or no water content. Observations of single-solvent droplets show that surprising quantities of gas molecules are trapped during rapid droplet growth. For example, CO2 is trapped at levels near 50 mol. % in droplets of acetone, tetrahydrofuran, or trimethylene oxide formed under CO2 pressures of several Torr in a cold-chamber at 170 K. Less but significant amounts of gas are trapped at higher temperatures, or in methanol or water-methanol droplets. The droplet metastability appears to commonly lead to formation of bubbles larger than the original nanodroplets. Besides serving as a guide for the all-vapor gas-hydrate studies, the semiquantitative evidence of extensive trapping of gases is expected to have a role in future studies of atmospheric aerosols.

Structures and energetics of hydrated deprotonated cis-pinonic acid anion clusters and their atmospheric relevance

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

Hou, Gao-Lei; Zhang, Jun; Valiev, Marat

2017-01-01

Pinonic acid, a C10-monocarboxylic acid with a hydrophilic –CO 2H group and a hydrophobic hydrocarbon backbone, is a key intermediate oxidation product of α-pinene – an important monoterpene compound in biogenic emission processes that influences the atmosphere. Molecular interaction between cis-pinonic acid and water is essential for understanding its role in the formation and growth of pinene-derived secondary organic aerosols. In this work, we studied the structures, energetics, and optical properties of hydrated clusters of cis-pinonate anion (cPA–), the deprotonated form of cis-pinonic acid, by negative ion photoelectron spectroscopy and ab initio theoretical calculations. Our results show that cPA– canmore » adopt two different structural configurations – open and folded. In the absence of waters, the open configuration has the lowest energy and provides the best agreement with the experiment. The addition waters, which mainly interact with the negatively charged -CO 2– group, gradually stabilize the folded configuration and lower its energy difference relative to the most stable open-configured structure. Thermochemical and equilibrium hydrate distribution analysis suggests that the mono- and di- hydrates are likely to exist in humid atmospheric environment with high populations. The detailed molecular description of cPA– hydrated clusters unraveled in this study provides a valuable reference for understanding the initial nucleation process and aerosol formation involving organics containing both hydrophilic and hydrophobic groups, as well as for analyzing the optical properties of those organic aerosols.« less

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 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.

Palagonitic Mars: A Basalt Centric View of Surface Composition and Aqueous Alteration

NASA Technical Reports Server (NTRS)

Morris, R. V.; Graff, T. G.; Ming, D. W.; Bell, J. F., III; Le, L.; Mertzman, S. A.; Christensen, P. R.

2004-01-01

Palagonitic tephra from certain areas on Mauna Kea Volcano (Hawaii) are well-established spectral and magnetic analogues of high-albedo regions on Mars. By definition, palagonite is "a yellow or orange isotropic mineraloid formed by hydration and devitrification of basaltic glass." The yellow to orange pigment is nanometer-sized ferric oxide particles (np-Ox) dispersed throughout the hydrated basaltic glass matrix. The hydration state of the np-Ox particles and the matrix is not known, but the best Martian spectral analogues contain allophane-like materials and not crystalline phyllosilicates. Martian low-albedo regions are also characterized by a palagonite-like ferric absorption edge, but, unlike the highalbedo regions, they also show evidence for absorption by ferrous iron. Thermal emission spectra (TES) obtained by the Mars Global Surveyor Thermal Emission Spectrometer suggest that basaltic (surface Type 1) and andesitic (surface Type 2) volcanic compositions preferentially occur in southern (Syrtis Major) and northern (Acidalia) hemispheres, respectively. The absence of a ferric-bearing component in the modeling of TES spectra is in apparent conflict with VNIR spectra of Martian dark regions, as discussed above. However, the andesitic spectra have also been interpreted as oxidized basalt using phyllosilicates instead of high-SiO2 glass as endmembers in the spectral deconvolution of surface Type 2 TES spectra. We show here that laboratory VNIR and TES spectra of rinds on basaltic rocks are spectral endmembers that provide a consistent explanation for both VNIR and TES data of Martian dark regions.

Water Sorption in Electron-Beam Evaporated SiO2 on QCM Crystals and Its Influence on Polymer Thin Film Hydration Measurements.

PubMed

Kushner, Douglas I; Hickner, Michael A

2017-05-30

Spectroscopic ellipsometry (SE) and quartz crystal microbalance (QCM) measurements are two critical characterization techniques routinely employed for hydration studies of polymer thin films. Water uptake by thin polymer films is an important area of study to investigate antifouling surfaces, to probe the swelling of thin water-containing ionomer films, and to conduct fundamental studies of polymer brush hydration and swelling. SiO 2 -coated QCM crystals, employed as substrates in many of these hydration studies, show porosity in the thin electron-beam (e-beam) evaporated SiO 2 layer. The water sorption into this porous SiO 2 layer requires correction of the optical and mass characterization of the hydrated polymer due to changes in the SiO 2 layer as it sorbs water. This correction is especially important when experiments on SiO 2 -coated QCM crystals are compared to measurements on Si wafers with dense native SiO 2 layers. Water adsorption filling void space during hydration in ∼200-260 nm thick SiO 2 layers deposited on a QCM crystal resulted in increased refractive index of the layer during water uptake experiments. The increased refractive index led to artificially higher polymer swelling in the optical modeling of the hydration experiments. The SiO 2 -coated QCM crystals showed between 6 and 8% void as measured by QCM and SE, accounting for 60%-85% of the measured polymer swelling in the low humidity regime (<20% RH) and 25%-40% of the polymer swelling in the high humidity regime (>70% RH) from optical modeling for 105 and 47 nm thick sulfonated polymer films. Correcting the refractive index of the SiO 2 layer for its water content resulted in polymer swelling that successfully resembled swelling measured on a silicon wafer with nonporous native oxide.

Authigenic carbonates from active methane seeps offshore southwest Africa

NASA Astrophysics Data System (ADS)

Pierre, Catherine; Blanc-Valleron, Marie-Madeleine; Demange, Jérôme; Boudouma, Omar; Foucher, Jean-Paul; Pape, Thomas; Himmler, Tobias; Fekete, Noemi; Spiess, Volkhard

2012-12-01

The southwest African continental margin is well known for occurrences of active methane-rich fluid seeps associated with seafloor pockmarks at water depths ranging broadly from the shelf to the deep basins, as well as with high gas flares in the water column, gas hydrate accumulations, diagenetic carbonate crusts and highly diverse benthic faunal communities. During the M76/3a expedition of R/V METEOR in 2008, gravity cores recovered abundant authigenic carbonate concretions from three known pockmark sites—Hydrate Hole, Worm Hole, the Regab pockmark—and two sites newly discovered during that cruise, the so-called Deep Hole and Baboon Cluster. The carbonate concretions were commonly associated with seep-benthic macrofauna and occurred within sediments bearing shallow gas hydrates. This study presents selected results from a comprehensive analysis of the mineralogy and isotope geochemistry of diagenetic carbonates sampled at these five pockmark sites. The oxygen isotope stratigraphy obtained from three cores of 2-5 m length indicates a maximum age of about 60,000-80,000 years for these sediments. The authigenic carbonates comprise mostly magnesian calcite and aragonite, associated occasionally with dolomite. Their very low carbon isotopic compositions (-61.0 < δ13C ‰ V-PDB < -40.1) suggest anaerobic oxidation of methane (AOM) as the main process controlling carbonate precipitation. The oxygen isotopic signatures (+2.4 < δ18O ‰ V-PDB < +6.2) lie within the range in equilibrium under present-day/interglacial to glacial conditions of bottom seawater; alternatively, the most positive δ18O values might reflect the contribution of 18O-rich water from gas hydrate decomposition. The frequent occurrence of diagenetic gypsum crystals suggests that reduced sulphur (hydrogen sulphide, pyrite) from sub-seafloor sediments has been oxidized by oxygenated bottom water. The acidity released during this process can potentially induce the dissolution of carbonate, thereby providing enough Ca2+ ions for pore solutions to reach gypsum saturation; this is thought to be promoted by the bio-irrigation and burrowing activity of benthic fauna. The δ18O-δ13C patterns identified in the authigenic carbonates are interpreted to reflect variations in the rate of AOM during the last glacial-interglacial cycle, in turn controlled by variably strong methane fluxes through the pockmarks. These results complement the conclusions of Kasten et al. in this special issue, based on authigenic barite trends at the Hydrate Hole and Worm Hole pockmarks which were interpreted to reflect spatiotemporal variations in AOM related to subsurface gas hydrate formation-decomposition.

Chemical composition and the potential for proteomic transformation in cancer, hypoxia, and hyperosmotic stress

PubMed Central

2017-01-01

The changes of protein expression that are monitored in proteomic experiments are a type of biological transformation that also involves changes in chemical composition. Accompanying the myriad molecular-level interactions that underlie any proteomic transformation, there is an overall thermodynamic potential that is sensitive to microenvironmental conditions, including local oxidation and hydration potential. Here, up- and down-expressed proteins identified in 71 comparative proteomics studies were analyzed using the average oxidation state of carbon (ZC) and water demand per residue (\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{upgreek} \\usepackage{mathrsfs} \\setlength{\\oddsidemargin}{-69pt} \\begin{document} }{}${\\overline{n}}_{{\\mathrm{H}}_{2}\\mathrm{O}}$\\end{document}n¯H2O), calculated using elemental abundances and stoichiometric reactions to form proteins from basis species. Experimental lowering of oxygen availability (hypoxia) or water activity (hyperosmotic stress) generally results in decreased ZC or \\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{upgreek} \\usepackage{mathrsfs} \\setlength{\\oddsidemargin}{-69pt} \\begin{document} }{}${\\overline{n}}_{{\\mathrm{H}}_{2}\\mathrm{O}}$\\end{document}n¯H2O of up-expressed compared to down-expressed proteins. This correspondence of chemical composition with experimental conditions provides evidence for attraction of the proteomes to a low-energy state. An opposite compositional change, toward higher average oxidation or hydration state, is found for proteomic transformations in colorectal and pancreatic cancer, and in two experiments for adipose-derived stem cells. Calculations of chemical affinity were used to estimate the thermodynamic potentials for proteomic transformations as a function of fugacity of O2 and activity of H2O, which serve as scales of oxidation and hydration potential. Diagrams summarizing the relative potential for formation of up- and down-expressed proteins have predicted equipotential lines that cluster around particular values of oxygen fugacity and water activity for similar datasets. The changes in chemical composition of proteomes are likely linked with reactions among other cellular molecules. A redox balance calculation indicates that an increase in the lipid to protein ratio in cancer cells by 20% over hypoxic cells would generate a large enough electron sink for oxidation of the cancer proteomes. The datasets and computer code used here are made available in a new R package, canprot. PMID:28603672

Mechanism of photocatalytic water oxidation on small TiO 2 nanoparticles

DOE PAGES

Muuronen, Mikko; Parker, Shane M.; Berardo, Enrico; ...

2016-12-07

Here, we present the first unconstrained nonadiabatic molecular dynamics (NAMD) simulations of photocatalytic water oxidation by small hydrated TiO 2 nanoparticles using Tully surface hopping and time-dependent density functional theory. The results indicate that ultrafast electron–proton transfer from physisorbed water to the photohole initiates the photo-oxidation on the S 1 potential energy surface. The new mechanism readily explains the observation of mobile hydroxyl radicals in recent experiments. Two key driving forces for the photo-oxidation reaction are identified: localization of the electron–hole pair and stabilization of the photohole by hydrogen bonding interaction. Our findings illustrate the scope of recent advances inmore » NAMD methods and emphasize the importance of explicit simulation of electronic excitations.« less

Innovations in Sampling Pore Fluids From Deep-Sea Hydrate Sites

NASA Astrophysics Data System (ADS)

Lapham, L. L.; Chanton, J. P.; Martens, C. S.; Schaefer, H.; Chapman, N. R.; Pohlman, J. W.

2003-12-01

We have developed a sea-floor probe capable of collecting and returning undecompressed pore water samples at in situ pressures for determination of dissolved gas concentrations and isotopic values in deep-sea sediments. In the summer of 2003, we tested this instrument in sediments containing gas hydrates off Vancouver Island, Cascadia Margin from ROPOS (a remotely operated vehicle) and in the Gulf of Mexico from Johnson-Sea-Link I (a manned submersible). Sediment push cores were collected alongside the probe to compare methane concentrations and stable carbon isotope compositions in decompressed samples vs. in situ samples obtained by probe. When sufficient gas was available, ethane and propane concentrations and isotopes were also compared. Preliminary data show maximum concentrations of dissolved methane to be 5mM at the Cascadia Margin Fish Boat site (850m water depth) and 12mM in the Gulf of Mexico Bush Hill hydrate site (550m water depth). Methane concentrations were, on average, five times as high in probe samples as in the cores. Carbon isotopic values show a thermogenic input and oxidative effects approaching the sediment-water interface at both sites. This novel data set will provide information that is critical to the understanding of the in situ processes and environmental conditions controlling gas hydrate occurrences in sediments.

Magnetic beads-based DNAzyme recognition and AuNPs-based enzymatic catalysis amplification for visual detection of trace uranyl ion in aqueous environment.

PubMed

Zhang, Hongyan; Lin, Ling; Zeng, Xiaoxue; Ruan, Yajuan; Wu, Yongning; Lin, Minggui; He, Ye; Fu, FengFu

2016-04-15

We herein developed a novel biosensor for the visual detection of trace uranyl ion (UO2(2+)) in aqueous environment with high sensitivity and specificity by using DNAzyme-functionalized magnetic beads (MBs) for UO2(2+) recognition and gold nano-particles (AuNPs)-based enzymatic catalysis oxidation of TMB (3,3',5,5'-tetramethylbenzidine sulfate) for signal generation. The utilization of MBs facilitates the magnetic separation and collection of sensing system from complex sample solution, which leads to more convenient experimental operation and more strong resistibility of the biosensor to the matrix of sample, and the utilization of AuNPs-based enzymatic catalysis amplification greatly improved the sensitivity of the biosensor. Compared with the previous DNAzyme-based UO2(2+) sensors, the proposed biosensor has outstanding advantages such as relative high sensitivity and specificity, operation convenience, low cost and more strong resistibility to the matrix of sample. It can be used to detect as low as 0.02 ppb (74 pM) of UO2(2+) in aqueous environment by only naked-eye observation and 1.89 ppt (7.0 pM) of UO2(2+) by UV-visible spectrophotometer with a recovery of 93-99% and a RSD ≤ 5.0% (n=6) within 3h. Especially, the visual detection limit of 0.02 ppb (74 pM) is much lower than the maximum allowable level of UO2(2+) (130 nM) in the drinking water defined by the U.S. Environmental Protection Agency (EPA), indicating that our method meets the requirement of rapid and on-site detection of UO2(2+) in the aqueous environment by only naked-eye observation. Copyright © 2015 Elsevier B.V. All rights reserved.

Topologically identical, but geometrically isomeric layers in hydrous α-, β-Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O and anhydrous Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})

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

Yu, Na; Klepov, Vladislav V.; Villa, Eric M.

2014-07-01

The hydrothermal reaction of uranyl nitrate with rubidium nitrate and arsenic (III) oxide results in the formation of polymorphic α- and β-Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O (α-, β-RbUAs) and the anhydrous phase Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})] (RbUAs). These phases were structurally, chemically and spectroscopically characterized. The structures of all three compounds are based upon topologically identical, but geometrically isomeric layers. The layers are linked with each other by means of the Rb cations and hydrogen bonding. Dehydration experiments demonstrate that water deintercalation from hydrous α- and β-RbUAs yields anhydrous RbUAs via topotactic reactions. - Graphical abstract: Three differentmore » layer geometries observed in the structures of Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})] and α- and β- Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O. Two different coordination environments of uranium polyhedra (types I and II) are shown schematically on the top of the figure. - Highlights: • Three new uranyl arsenates were synthesized from the hydrothermal reactions. • The phases consist of the topologically identical but geometrically different layers. • Topotactic transitions were observed in the processes of mono-hyrates dehydration.« less

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.

Biogenic uraninite precipitation and its reoxidation by iron(III) (hydr)oxides: A reaction modeling approach

NASA Astrophysics Data System (ADS)

Spycher, Nicolas F.; Issarangkun, Montarat; Stewart, Brandy D.; Sevinç Şengör, S.; Belding, Eileen; Ginn, Tim R.; Peyton, Brent M.; Sani, Rajesh K.

2011-08-01

One option for immobilizing uranium present in subsurface contaminated groundwater is in situ bioremediation, whereby dissimilatory metal-reducing bacteria and/or sulfate-reducing bacteria are stimulated to catalyze the reduction of soluble U(VI) and precipitate it as uraninite (UO 2). This is typically accomplished by amending groundwater with an organic electron donor. It has been shown, however, that once the electron donor is entirely consumed, Fe(III) (hydr)oxides can reoxidize biogenically produced UO 2, thus potentially impeding cleanup efforts. On the basis of published experiments showing that such reoxidation takes place even under highly reducing conditions (e.g., sulfate-reducing conditions), thermodynamic and kinetic constraints affecting this reoxidation are examined using multicomponent biogeochemical simulations, with particular focus on the role of sulfide and Fe(II) in solution. The solubility of UO 2 and Fe(III) (hydr)oxides are presented, and the effect of nanoscale particle size on stability is discussed. Thermodynamically, sulfide is preferentially oxidized by Fe(III) (hydr)oxides, compared to biogenic UO 2, and for this reason the relative rates of sulfide and UO 2 oxidation play a key role on whether or not UO 2 reoxidizes. The amount of Fe(II) in solution is another important factor, with the precipitation of Fe(II) minerals lowering the Fe +2 activity in solution and increasing the potential for both sulfide and UO 2 reoxidation. The greater (and unintuitive) UO 2 reoxidation by hematite compared to ferrihydrite previously reported in some experiments can be explained by the exhaustion of this mineral from reaction with sulfide. Simulations also confirm previous studies suggesting that carbonate produced by the degradation of organic electron donors used for bioreduction may significantly increase the potential for UO 2 reoxidation through formation of uranyl carbonate aqueous complexes.

Different pattern of brain pro-/anti-oxidant activity between depleted and enriched uranium in chronically exposed rats.

PubMed

Lestaevel, P; Romero, E; Dhieux, B; Ben Soussan, H; Berradi, H; Dublineau, I; Voisin, P; Gourmelon, P

2009-04-05

Uranium is not only a heavy metal but also an alpha particle emitter. The main toxicity of uranium is expected to be due to chemiotoxicity rather than to radiotoxicity. Some studies have demonstrated that uranium induced some neurological disturbances, but without clear explanations. A possible mechanism of this neurotoxicity could be the oxidative stress induced by reactive oxygen species imbalance. The aim of the present study was to determine whether a chronic ingestion of uranium induced anti-oxidative defence mechanisms in the brain of rats. Rats received depleted (DU) or 4% enriched (EU) uranyl nitrate in the drinking water at 2mg(-1)kg(-1)day(-1) for 9 months. Cerebral cortex analyses were made by measuring mRNA and protein levels and enzymatic activities. Lipid peroxidation, an oxidative stress marker, was significantly enhanced after EU exposure, but not after DU. The gene expression or activity of the main antioxidant enzymes, i.e. superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPx), increased significantly after chronic exposure to DU. On the contrary, oral EU administration induced a decrease of these antioxidant enzymes. The NO-ergic pathway was almost not perturbed by DU or EU exposure. Finally, DU exposure increased significantly the transporters (Divalent-Metal-Transporter1; DMT1), the storage molecule (ferritin) and the ferroxidase enzyme (ceruloplasmin), but not EU. These results illustrate that oxidative stress plays a key role in the mechanism of uranium neurotoxicity. They showed that chronic exposure to DU, but not EU, seems to induce an increase of several antioxidant agents in order to counteract the oxidative stress. Finally, these results demonstrate the importance of the double toxicity, chemical and radiological, of uranium.

77 FR 74025 - Federated Indians of Graton Rancheria-Liquor Control Statute

Federal Register 2010, 2011, 2012, 2013, 2014

2012-12-12

..., hydrated oxide of ethyl, or spirit of wine, in any form, and regardless of source or the process used for its production. (b) Alcoholic beverage means all alcohol, spirits, liquor, wine, beer and any liquid or solid containing alcohol, spirits, liquor, wine, or beer, and which contains one-half of one...

Bioelectrochemical propulsion.

PubMed

Mano, Nicolas; Heller, Adam

2005-08-24

A carbon fiber having a terminal glucose oxidizing microanode and an O2 reducing microcathode is propelled at the water-O2 interface. The electron current in the fiber is accompanied by a flux of hydrated protons that is so fast at the solution-air interface, where the viscous drag is small, that the fiber's velocity is 1 cm s-1.

3-Dimensional Computational Fluid Dynamics Modeling of Solid Oxide Fuel Cell Using Different Fuels

DTIC Science & Technology

2011-01-01

major types of fuel cells in practice are listed below: Polymer Electrolyte Membrane Fuel Cell ( PEMFC ) Alkaline Fuel cell (AFC) Phosphoric Acid...Material Operating Temperature (oC) Efficiency (%) PEMFC H2, Methanol, Formic Acid Hydrated Organic Polymer < 90 40-50 AFC Pure H2 Aqueous

77 FR 21581 - Kootenai Tribe of Idaho: Chapter 11-Alcohol Control Act

Federal Register 2010, 2011, 2012, 2013, 2014

2012-04-10

..., hydrated oxide of ethyl, or spirit of wine, which is produced by the fermentation or distillation of grain..., flavored malt beverages such as wine coolers, obtained by the alcoholic fermentation of an infusion or...) ``Wine'' means any alcoholic beverage obtained by fermentation of fruits or other agricultural products...

Dynamics of Water Associated with Lithium Ions Distributed in Polyethylene Oxide

DOE PAGES

Zhang, Zhe; Ohl, Michael; Diallo, Souleymane O.; ...

2015-11-03

We studied the dynamics of water in polyethylene oxide (PEO)/LiCl solution with quasielastic neutron scattering experiments and molecular dynamics (MD) simulations. Two different time scales of water diffusion representing interfacial water and bulk water dynamics have been identified. Furthermore, the measured diffusion coefficient of interfacial water remained 5–10 times smaller than that of bulk water, but both were slowed by approximately 50% in the presence of Li +. Detailed analysis of MD trajectories suggests that Li + is favorably found at the surface of the hydration layer, and the probability to find the caged Li + configuration formed by themore » PEO is lower than for the noncaged Li +-PEO configuration. In both configurations, however, the slowing down of water molecules is driven by reorienting water molecules and creating water-Li + hydration complexes. Moreover, performing the MD simulation with different ions (Na + and K +) revealed that smaller ionic radius of the ions is a key factor in disrupting the formation of PEO cages by allowing spaces for water molecules to come in between the ion and PEO.« less

Dynamics of Water Associated with Lithium Ions Distributed in Polyethylene Oxide

NASA Astrophysics Data System (ADS)

Zhang, Zhe; Ohl, Michael; Diallo, Souleymane O.; Jalarvo, Niina H.; Hong, Kunlun; Han, Youngkyu; Smith, Gregory S.; Do, Changwoo

2015-11-01

The dynamics of water in polyethylene oxide (PEO)/LiCl solution has been studied with quasielastic neutron scattering experiments and molecular dynamics (MD) simulations. Two different time scales of water diffusion representing interfacial water and bulk water dynamics have been identified. The measured diffusion coefficient of interfacial water remained 5-10 times smaller than that of bulk water, but both were slowed by approximately 50% in the presence of Li+ . Detailed analysis of MD trajectories suggests that Li+ is favorably found at the surface of the hydration layer, and the probability to find the caged Li+ configuration formed by the PEO is lower than for the noncaged Li+-PEO configuration. In both configurations, however, the slowing down of water molecules is driven by reorienting water molecules and creating water-Li+ hydration complexes. Performing the MD simulation with different ions (Na+ and K+ ) revealed that smaller ionic radius of the ions is a key factor in disrupting the formation of PEO cages by allowing spaces for water molecules to come in between the ion and PEO.

Dynamics of Water Associated with Lithium Ions Distributed in Polyethylene Oxide.

PubMed

Zhang, Zhe; Ohl, Michael; Diallo, Souleymane O; Jalarvo, Niina H; Hong, Kunlun; Han, Youngkyu; Smith, Gregory S; Do, Changwoo

2015-11-06

The dynamics of water in polyethylene oxide (PEO)/LiCl solution has been studied with quasielastic neutron scattering experiments and molecular dynamics (MD) simulations. Two different time scales of water diffusion representing interfacial water and bulk water dynamics have been identified. The measured diffusion coefficient of interfacial water remained 5-10 times smaller than that of bulk water, but both were slowed by approximately 50% in the presence of Li(+). Detailed analysis of MD trajectories suggests that Li(+) is favorably found at the surface of the hydration layer, and the probability to find the caged Li(+) configuration formed by the PEO is lower than for the noncaged Li(+)-PEO configuration. In both configurations, however, the slowing down of water molecules is driven by reorienting water molecules and creating water-Li(+) hydration complexes. Performing the MD simulation with different ions (Na(+) and K(+)) revealed that smaller ionic radius of the ions is a key factor in disrupting the formation of PEO cages by allowing spaces for water molecules to come in between the ion and PEO.

Reaction Kinetics and Combustion Dynamics of I4O9 and Aluminum Mixtures

PubMed Central

Smith, Dylan K.; Pantoya, Michelle L.; Parkey, Jeffrey S.; Kesmez, Mehmet

2016-01-01

Tetraiodine nonoxide (I4O9) has been synthesized using a dry approach that combines elemental oxygen and iodine without the introduction of hydrated species. The synthesis approach inhibits the topochemical effect promoting rapid hydration when exposed to the relative humidity of ambient air. This stable, amorphous, nano-particle material was analyzed using differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) and showed an exothermic energy release at low temperature (i.e., 180 °C) for the transformation of I4O9 into I2O5. This additional exothermic energy release contributes to an increase in overall reactivity of I4O9 when dry mixed with nano-aluminum (Al) powder, resulting in a minimum of 150% increase in flame speed compared to Al + I2O5. This study shows that as an oxidizer, I4O9 has more reactive potential than other forms of iodine(V) oxide when combined with Al, especially if I4O9 can be passivated to inhibit absorption of water from its surrounding environment. PMID:27842354

Understanding Surface Processes on Mars Through Study of Iron Oxides/Oxyhydroxides: Clues to Surface Alteration and Aqueous Processes

NASA Technical Reports Server (NTRS)

Bishop, J. L.; Mancinelli, R. L.; Dyar, M. D.; Parente, M.; Drief, A.; Lane, M. D.; Murad, E.

2006-01-01

We are performing oxidation and reduction reactions on hydrated ferric oxide minerals in order to investigate how these might alter under a variety of conditions on the surface of Mars. Preliminary experiments on ferrihydrite and goethite showed that heating these minerals in a dry oxidizing environment produces fine-grained hematite, while heating these minerals in a reducing environment produces fine-grained magnetite. Under Mars-like oxidation levels this magnetite then oxidizes to maghemite. These reactions are dependent on the presence of water and organic material that can act as a reductant. We are using reflectance and Mossbauer spectroscopy to characterize the reaction products and TEM to analyze the sample texture. Our preliminary results indicate that magnetite and maghemite could be formed in the soil on Mars from ferrihydrite and goethite if organics were present on early Mars.

Water exchange in manganese-based water-oxidizing catalysts in photosynthetic systems: from the water-oxidizing complex in photosystem II to nano-sized manganese oxides.

PubMed

Najafpour, Mohammad Mahdi; Isaloo, Mohsen Abbasi; Eaton-Rye, Julian J; Tomo, Tatsuya; Nishihara, Hiroshi; Satoh, Kimiyuki; Carpentier, Robert; Shen, Jian-Ren; Allakhverdiev, Suleyman I

2014-09-01

The water-oxidizing complex (WOC), also known as the oxygen-evolving complex (OEC), of photosystem II in oxygenic photosynthetic organisms efficiently catalyzes water oxidation. It is, therefore, responsible for the presence of oxygen in the Earth's atmosphere. The WOC is a manganese-calcium (Mn₄CaO₅(H₂O)₄) cluster housed in a protein complex. In this review, we focus on water exchange chemistry of metal hydrates and discuss the mechanisms and factors affecting this chemical process. Further, water exchange rates for both the biological cofactor and synthetic manganese water splitting are discussed. The importance of fully unveiling the water exchange mechanism to understand the chemistry of water oxidation is also emphasized here. This article is part of a special issue entitled: photosynthesis research for sustainability: keys to produce clean energy. Copyright © 2014 Elsevier B.V. All rights reserved.

Selective tuning of the self-assembly and gelation of a hydrophilic poloxamine by cyclodextrins.

PubMed

González-Gaitano, Gustavo; da Silva, Marcelo A; Radulescu, Aurel; Dreiss, Cécile A

2015-05-26

Complexes formed between cyclodextrins (CDs) and polymers - pseudopolyrotaxanes (PPRs) - are the starting point of a multitude of supramolecular structures, which are proposed for a wide range of biomedical and technological applications. In this work, we investigate the complexation of a range of cyclodextrins with Tetronic T1307, a four-arm block copolymer of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) with a pH-responsive central ethylene diamine spacer, and its impact on micellization and the sol-gel transition. At low concentrations, small-angle neutron scattering (SANS) combined with dynamic light scattering (DLS) measurements show the presence of spherical micelles with a highly hydrated shell and a dehydrated core. Increasing the temperature leads to more compact micelles and larger aggregation numbers, whereas acidic conditions induce a shrinking of the micelles, with fewer unimers per micelle and a more hydrated corona. At high concentrations, T1307 undergoes a sol-gel transition, which is suppressed at pH below the pKa,1 (4.6). SANS data analysis reveals that the gels result from a random packing of the micelles, which have an increasing aggregation number and increasingly dehydrated shell and hydrated core with the temperature. Native CDs (α, β, γ-CD) can complex T1307, resulting in the precipitation of a PPR. Instead, modified CDs compete with micellization to an extent that is critically dependent on the nature of the substitution. (1)H and ROESY NMR combined with SANS demonstrate that dimethylated β-CD can thread onto the polymer, preferentially binding to the PO units, thus hindering self-aggregation by solubilizing the hydrophobic block. The various CDs are able to modulate the onset of gelation and the extent of the gel phase, and the effect correlates with the ability of the CDs to disrupt the micelles, with the exception of a sulfated sodium salt of β-CD, which, while not affecting the CMT, is able to fully suppress the gel phase.

Dynamic processes occurring at the Cr IIIaq-manganite (γ-MnOOH) interface: simultaneous adsorption, microprecipitation, oxidation/reduction, and dissolution

NASA Astrophysics Data System (ADS)

Weaver, Robert M.; Hochella, Michael F.; Ilton, Eugene S.

2002-12-01

The complex interaction between Cr IIIaq and manganite (γ-MnOOH) was systematically studied at room temperature over a pH range of 3 to 6, and within a concentration range of 10 -4 to 10 -2 M CrOH 2+aq. Solution compositional changes during batch reactions were characterized by inductively coupled plasma spectroscopy and ultraviolet-visible spectrophotometry. The manganites were characterized before and after reaction with X-ray photoelectron spectroscopy, scanning electron microscopy (SEM), high-resolution field-emission SEM, and energy-dispersive spectroscopy analysis. Fluid-cell atomic force microscopy was used to follow these metal-mineral interactions in situ. The reactions are characterized by (1) sorption of Cr III and the surface-catalyzed microprecipitation of Cr III-hydroxy hydrate on manganite surfaces, (2) the acidic dissolution of the manganite, and (3) the simultaneous reductive dissolution of manganite coupled with the oxidation of Cr IIIaq to highly toxic Cr VIaq. Cr III-hydroxy hydrate was shown to precipitate on the manganite surface while still undersaturated in bulk solution. The rate of manganite dissolution increased with decreasing pH due both to acid-promoted and Mn-reduction-promoted dissolution. Cr oxidation also increased in the lower pH range, this as a result of its direct redox coupling with Mn reduction. Neither Mn II nor Cr VI were ever detected on manganite surfaces, even at the maximum rate of their generation. At the highest pHs of this study, Cr IIIaq was effectively removed from solution to form Cr III-hydroxy hydrate on manganite surfaces and in the bulk solution, and manganite dissolution and Cr VIaq generation were minimized. All interface reactions described above were heterogeneous across the manganite surfaces. This heterogeneity is a direct result of the heterogeneous semiconducting nature of natural manganite crystals and is also an expression of the proximity effect, whereby redox processes on semiconducting surfaces are not limited to next nearest neighbor sites.

C-H functionalization of 1,4-naphthoquinone by oxidative coupling with anilines in the presence of a catalytic quantity of copper(II) acetate.

PubMed

Lisboa, Cinthia da S; Santos, Vanessa G; Vaz, Boniek G; de Lucas, Nanci C; Eberlin, Marcos N; Garden, Simon J

2011-07-01

The oxidative addition of anilines (2) with 1,4-naphthoquinone (3) to give N-aryl-2-amino-1,4-naphthoquinones (1) was found to be catalyzed by copper(II) acetate. In the absence of the catalyst, the reactions are slower and give lower yields with the formation of many colateral products. In the presence of 10 mol % hydrated copper(II) acetate, the reactions are generally more efficient in that they are cleaner, higher yielding, and faster.

Thermal decomposition kinetics of hydrazinium cerium 2,3-Pyrazinedicarboxylate hydrate: a new precursor for CeO2.

PubMed

Premkumar, Thathan; Govindarajan, Subbiah; Coles, Andrew E; Wight, Charles A

2005-04-07

The thermal decomposition kinetics of N(2)H(5)[Ce(pyrazine-2,3-dicarboxylate)(2)(H(2)O)] (Ce-P) have been studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), for the first time; TGA analysis reveals an oxidative decomposition process yielding CeO(2) as the final product with an activation energy of approximately 160 kJ mol(-1). This complex may be used as a precursor to fine particle cerium oxides due to its low temperature of decomposition.

Effect of Graphene Oxide on Mechanical Properties of Recycled Mortar

NASA Astrophysics Data System (ADS)

Fang, Changle; Long, Wujian; Wei, Jingjie; Xiao, Bingxu; Yan, Chen

2017-12-01

The use of recycled aggregate as replacement of natural aggregate has increased in recent years in order to reduce the high consumption of natural resources in construction industry. This paper presents an experimental investigation on the effect of graphene oxide (GO) on the mechanical properties of recycled mortar. It is showed that the recycled mortar with GO has a better mechanical properties than the recycled mortar without GO. Microstructural analysis of the recycled mortar with GO showed to have much denser and better crystallization of hydration product.

Hydrogenation of liquid natural rubber via diimide reduction in hydrazine hydrate/hydrogen peroxide system

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

Yusof, Muhammad Jefri Mohd; Jamaluddin, Naharullah; Abdullah, Ibrahim

Liquid natural rubber (LNR) with molecular weight of lower than 10{sup 5} and shorter polymeric chain than natural rubber was prepared. LNR was then hydrogenated via diimide reduction by oxidation of hydrazine hydrate with hydrogen peroxide. The unsaturated units of the rubber were converted into saturated hydrocarbon to strengthen the backbone of the polymer so it was able to resist thermal degradation. The results indicated that hydrogenation degree of the product (HLNR) could be extended to 91.2% conversion under appropriate conditions. The hydrogenated LNR (HLNR) was characterized using Fourier-Transform Infrared (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopy. The physical characteristicsmore » of HLNR were analyzed with Termogravimetric Analysis (TGA)« less

The influence of different modified graphene on property of DSSCs

NASA Astrophysics Data System (ADS)

Xu, Kai; Shen, Yue; Zhang, Zongkun; Cao, Meng; Gu, Feng; Wang, Linjun

2016-01-01

Two kinds of modified reduced graphene oxide (rGO) power with different hydrophilic property were synthesized in NH3/hydrazine hydrate (N-rGO) and KOH/hydrazine hydrate (K-rGO) reduction systems, respectively, and be used as counter electrode materials. The as-prepared rGO counter electrodes were confirmed as substitution for Pt counter electrode in dye-sensitized solar cells (DSSCs). The efficiency (η) of DSSCs based on N-rGO counter electrodes achieved 4.72% while that of K-rGO counter electrode was just 3.38%. The electrochemical impedance spectroscopy (EIS) measurements revealed that the hydrophilic K-rGO counter electrode has a low charge transfer resistance (Rct) and the hydrophobic N-rGO counter electrode has a low series resistance (Rs).

Characterization of the transient species generated by the photoionization of Berberine: A laser flash photolysis study

NASA Astrophysics Data System (ADS)

Cheng, Ling-Li; Wang, Mei; Zhu, Hui; Li, Kun; Zhu, Rong-Rong; Sun, Xiao-Yu; Yao, Si-De; Wu, Qing-Sheng; Wang, Shi-Long

2009-09-01

Using 266 nm laser flash photolysis it has been demonstrated that Berberine (BBR) in aqueous solution is ionized via a mono-photonic process giving a hydrated electron, anion radical that formed by hydrated electron react with steady state of BBR, and neutral radical that formed from rapid deprotonation of the radical cation of BBR. The quantum yield of photoionization is determined to be 0.03 at room temperature with KI solution used as a reference. Furthermore utilizing pH changing method and the SO 4rad - radical oxidation method, the assignment of radical cation of BBR was further confirmed, the p Ka value of it was calculated, and the related set up rate constant was also determined.

The betainic form of (imidazol-2-yl)phenylphosphinic acid hydrate

PubMed Central

Kunz, Peter C.; Frank, Walter

2010-01-01

Single crystals of the title compound, (imidazolium-2-yl)phenyl­phosphinate monohydrate, C9H9N2O2·H2O, were ob­tained from methanol/water after deprotection and oxidation of bis­(1-diethoxy­methyl­imidazol-2-yl)phenyl­phosphane. In the structure, several N–H⋯O and P—O⋯H–O hydrogen bonds are found. π–π inter­actions between the protonated imidazolyl rings [centroid–centroid distance = 3.977 (2) Å] help to establish the crystal packing. The hydrate water mol­ecule builds hydrogen bridges to three mol­ecules of the phosphinic acid by the O and both H atoms. PMID:21579513

Solution Conformations of Graphene Oxide Sheets, and Two-Dimensional Nanofluidics

NASA Astrophysics Data System (ADS)

Koltonow, Andrew R.

This work reports studies on the physical properties of collections of nanosheets. First, the configurations of graphene oxide sheets in solution are studied. Polarized optical microscopy reveals quickly and decisively that sheets remain flat and form lyotropic liquid crystals over a wide range of solvent conditions. When solvent conditions are inhospitable enough, sheets agglomerate into stacks rather crumpling upon themselves. Theory and simulation suggest that the crumpled state, which can be formed by compressing sheets, is metastable. This work might correct a persistent misunderstanding about the solution physics of graphene oxide. The other major area of study concerns the hydration layers in between lamellar stacks of exfoliated, restacked nanosheets. These layers comprise massive arrays of parallel two-dimensional nanofluidic channels, which exhibit enhanced unipolar ionic conductivity with counterions as the majority charge carriers. Based on the previously discovered graphene oxide nanofluidic platform, exfoliated vermiculite nanofluidic channels are constructed, which shuttle protons through the hydration channels by a Grotthuss mechanism, and which show superior thermal stability to graphene oxide. The 2D nanofluidics platform is also used to demonstrate "kirigami nanofluidics", where ion transport can be manipulated by cutting the film into specific shapes. This can give rise to ionic current rectification. The rectification effect is attributed to the size and shape mismatch of the concentration polarization zones developed at the inlets and outlets of the nanofluidic channels. The kirigami nanofluidic platform can be used to fabricate ionic diodes and other simple devices. This material platform is expected to be a useful tool for nanofluidics researchers, because it offers a way to carry out nanofluidic experiments quickly with minimal equipment and little expense.

Nano-encapsulation of Dietary Phytoconstituent Capsaicin on Emulsome: Evaluation of Anticancer Activity Through the Measurement of Liver Oxidative Stress in Rats.

PubMed

Giri, Tapan K; Pramanik, Kaustav; Barman, Tapan K; Maity, Subhasis

2017-01-01

Excessive reactive species derived from oxygen and nitrogen leads to oxidative damage to tissue and organs. Capsaicin (CAP), a pungent component found in red pepper can prevent oxidative stress. The aim of the present work was to evaluate the protective effects of CAP loaded nano-emulsomes (EML) against the oxidative stress of rat livers induced through sodium fluoride (NaF). EML was prepared by thin film hydration method that is development of thin lipid film followed by hydration and sonication. EML was characterized by Fourier transform infrared (FT-IR) spectroscopy and X-ray diffraction (XRD) techniques. EML was evaluated for drug entrapment, in vitro drug release, and in vivo study. In vitro drug release study of optimized formulation showed that 50% of CAP was released within 50.21 min while 85% CAP was released in 227.4 min. Single oral dose of free CAP and CAP loaded EML were given to rats 2 hour after NaF administration. Membrane of hepatic cells was damaged by NaF and it was judged by the estimation of lipid peroxidation, reactive oxygen species (ROS), and catalase activity. The administration of CAP loaded EML 2 hr after NAF consumption showed significant decrease in ROS level compared to free CAP. EML containing CAP was more effective in comparison to free CAP in controlling the lipid peroxidation that is thiobarbituric acid substance augmentation in liver by the treatment of NaF. The administration of CAP loaded EML showed significant increase in catalase activity compared to free CAP administration. The results clearly demonstrated that CAP loaded EML may be accepted as an effective therapeutic formulation in preventing oxidative damage. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

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.

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.

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.

A cheaper, faster, better way to detect water of hydration on Solar System bodies

NASA Technical Reports Server (NTRS)

Vilas, Faith

1994-01-01

The 3.0-micrometers water of hydration absorption feature observed in the IR photometry of many low-albedo and some medium-albedo asteroids strongly correlates with the 0.7-micrometers Fe(+2) to Fe(+3) oxidized iron absorption feature observed in narrowband spectrophotometry of these asteroids. Using this relationship, an empirical algorithm for predicting the presence of water of hydration in the surface material of a Solar System body using photometry obtained through the Eight-Color Asteroid Survey nu (0.550 micrometers), w (0.701 micrometers), and x (0.853 micrometers) filters was developed and applied to the ECAS photometry of asteroids and outer planet satellites. The percentage of objects in low-albedo, outer main-belt asteroid classes that test positively for water of hydration increases from P to B to C to G class and correlates linearly with the increasing mean albedos of those objects testing positively. The medium-albedo M-class asteroids do not test positively in large number using this algorithm. Aqueously altered asteroids dominate the Solar System population between heliocentric distances of 2.6 to 3.5 AU, bracketing the Solar System region where the aqueous alteration mechanism operated most strongly. One jovian satellite, J VI Himalia, and one saturnian satellite. Phoebe, tested positively for water of hydration, supporting the hypothesis that these may be captured C-class asteroids from a postaccretional dispersion. The proposed testing technique could be applied to an Earth-based survey of asteroids or a space-probe study of an asteroid's surface characteristic in order to identify a potential water source.