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Sample records for perrhenates

  1. Electrodialysis synthesis of concentrated solutions of perrhenic acid

    NASA Astrophysics Data System (ADS)

    Palant, A. A.; Bryukvin, V. A.; Levin, A. M.; Reshetova, O. V.

    2011-03-01

    The presented results demonstrate the possibility of electrodialysis production of concentrated solutions of perrhenic acid (HReO4 concentration >400 g/l). KReO4 is used as a precursor. The investigations are performed in a three-chamber electrodialysis cell in a continuous mode. The optimal processing parameters are as follows: the current is 3-5 A, the voltage is 30-40 V, and the anode chamber temperature is 20-25°C. Grade AR-0 ammonium perrhenate is precipitated from the obtained HReO4 solution.

  2. Preparation of 186Re-perrhenate for nuclear medical purposes.

    PubMed

    Eisenhut, M

    1982-02-01

    The preparation of 186Re perrhenic acid from metallic rhenium-186 is achieved by the oxidation of 186Re with H2O2. Neutralization with aqueous ammonia and evaporation of the solvent yielded pure NH4 186ReO4. As an example of its applicability to nuclear medicine the 186Re-MDP complex was formed by the tin-reduction method and tested for its bone affinity in rabbits. The 186Re-MDP complex formation proved to be pH dependent, with almost no 186Re-MDP complex being formed at neutral pH whereas 92.6% of the nuclide was complexed to MDP at pH 1.4 indicating the necessity for a sufficiently low pH for rapid 186Re-complex formation. PMID:7061167

  3. Evaluation of Perrhenate Spectrophotometric Methods in Bicarbonate and Nitrate Media.

    PubMed

    Lenell, Brian A; Arai, Yuji

    2016-04-01

    2-pyridyl thiourea and methyl-2-pyridyl ketoxime based perrhenate, Re(VII), UV-vis spectrophotometric methods were evaluated in nitrate and bicarbonate solutions ranging from 0.001 M to 0.5 M. Standard curves at [Re]=2.5-50 mg L(-1) for the Re(IV)-thiourea and the Re ketoxime complexes were constructed at 405 nm and 490 nm, respectively. Detection of limits for N-(2-pyridyl) thiourea and methyl-2-pyridyl ketoxime methods in ultrapure water are 3.06 mg/L and 4.03 mg/L, respectively. Influences of NaHCO3 and NaNO3 concentration on absorbance spectra, absorptivity, and linearity were documented. For both methods, samples in ultrapure water and NaHCO3 have an R(2) value>0.99, indicating strong linear relationships. Statistical analysis supports that NaHCO3 does not affect linearity between standards for either method. NaNO3 causes major interference with the ketoxime method above 0.001 M NaNO3. Data provides information for practical use of Re spectrophotometric methods in environmental media that is high in bicarbonate and nitrate. PMID:26838460

  4. Perrhenate extraction studies by Cyphos 101-IL; screening for implementation in technetium removal

    SciTech Connect

    Mark D Ogden; Sarah E. Pepper

    2013-10-01

    The solvent extraction of rhenium (VII) from chloride solutions by Cyphos 101-IL in toluene has been studied. Distribution values for the extraction of perrhenate are extremely high leading to almost quantitative extraction. From slope analysis, an anion exchange extraction mechanism is proposed, with formation of a ReO4 association with one Cyphos IL-101 cation. The extraction kinetics are fast, with complete equilibration occurring within 60 s. Under identical conditions, distribution coefficients for Cyphos 101-IL are greater than for Aliquat-336. Extraction of the perrhenate anion does not seem to be negatively impacted by common environmental contaminants including iron, sulphate and nitrate at the pH values tested.

  5. Synthesis and Characterization of Periodic Mesoporous Organosilicas as Anion-Exchance Resins for Perrhenate Adsorption.

    SciTech Connect

    Lee, Byunghwan; Im, Hee-Jung; Luo, Huimin; Hagaman, Edward {Ed} W; Dai, Sheng

    2005-01-01

    A new methodology to immobilize ionic liquids through the use of a bridged silsesquioxane N-(3-triethoxysilylpropyl), N(3)-3-trimethoxysilylpropyl-4,5-dihydroimidazolium iodide that incorporates an ionic functionality for the assembly of novel periodic mesoporous organosilica (PMO) materials has been developed. The resulting PMO materials were investigated for use as novel anion exchange resins for the separation of perrhenate anions in aqueous solution. As compared with cetyltrimethylammonium chloride, 1-hexadecane-3-methylimidazolium bromide has been demonstrated to be a more efficient surfactant template for the generation of mesopores and surface areas for such PMO materials.

  6. A comprehensive study on the blockage of thyroid and gastric uptakes of 188Re-perrhenate in endovascular irradiation using liquid-filled balloon to prevent restenosis.

    PubMed

    Lin, W Y; Hsieh, J F; Tsai, S C; Yen, T C; Wang, S J; Knapp, F F

    2000-01-01

    188Re-perrhenate has been reported effective in preventing restenosis after percutaneous transluminal coronary angioplasty. However, if the balloon ruptures, 188Re-perrhenate is released into the circulation, causing high radiation dosing to the thyroid and stomach. In this study, we evaluated the effects of perchlorate or iodide given at different times and in different ways for blocking the uptake of 188Re-perrhenate in the thyroid glands and the stomach to find the best method to apply clinically to reduce the radiation dose in case of balloon rupture. Sodium perchlorate, sodium iodide, or potassium iodide was given orally or intravenously to rats before, during, and after the injection of 188Re-perrhenate. The rats were sacrificed and we calculated the concentration of 188Re-perrhenate in various organs to evaluate the preblocking, mixed formula, and postblocking effects of perchlorate or iodide. Our data showed that the preblocking method effectively reduced the uptake of 188Re-perrhenate in both the thyroid and the stomach. The mixed formula method also demonstrated good blocking effect. The postblocking method showed obvious depression of thyroid uptake of perrhenate but its blocking effect on the stomach was not satisfactory. PMID:10755650

  7. Raman Analysis of Perrhenate and Pertechnetate in Alkali Salts and Borosilicate Glasses

    SciTech Connect

    Gassman, Paul L.; McCloy, John S.; Soderquist, Chuck Z.; Schweiger, Michael J.

    2014-01-03

    Sodium borosilicate glasses containing various concentrations of rhenium or technetium were fabricated, and their vibrational spectra studied using a Raman microscope. Spectra were interpreted with reference to new high resolution measurements of alkali pertechnetates and perrhenates NaReO4, KReO4, NaTcO4, and KTcO4. At low concentrations of ReO4- or TcO4-, glass spectra show weak peaks superimposed on a dominant spectrum of glass characteristic of silicate and borate network vibrations. At high concentrations, sharp peaks characteristic of crystal field splitting and C4h symmetry dominate the spectra of glasses, indicating alkali nearby tetrahedral Re or Tc. Often peaks indicative of both the K and Na pertechnetates/ perrhenates are evident in the Raman spectrum, with the latter being favored at high additions of the source chemical, since Na is more prevalent in the glass and ion exchange takes place. These results have significance to immobilization of nuclear waste containing radioactive 99Tc in glass for ultimate disposal.

  8. A Hexameric Cationic Copper(II) Metallacrown as a Pertechnetate and Perrhenate Scavenger.

    PubMed

    Rodríguez-Hermida, Sabina; Lago, Ana Belén; Pino-Cuevas, Arantxa; Hagenbach, Adelheid; Cañadillas-Delgado, Laura; Carballo, Rosa; Abram, Ulrich; Vázquez-López, Ezequiel M

    2016-01-26

    Materials based on the cationic copper(II) hexanuclear 18-membered metallacrown [18-MCCuII-N(2ph)-6](6+) (2phH=2-piconyl hydrazide) and tetrafluoroborate, perchlorate, nitrate, sulfate, and perrhenate anions were prepared by an easy method in aqueous medium. Single-crystal X-ray characterization of six members of this new family of complexes showed that the anions are attached to the metallacrown by direct coordination to a copper cation or by hydrogen-bonding interaction with the center of the hexamer. The stable cationic nature of the complexes and their ability to bind different anions allows them to adsorb and immobilize environmentally relevant anions such as MO4(-) (M=Tc, Re). The MO4(-) trapping capacities suggest that these materials would be useful in the treatment of oxoanionic contaminants in water. PMID:26671639

  9. Zirconium-Based Metal-Organic Framework for Removal of Perrhenate from Water.

    PubMed

    Banerjee, Debasis; Xu, Wenqian; Nie, Zimin; Johnson, Lewis E V; Coghlan, Campbell; Sushko, Maria L; Kim, Dongsang; Schweiger, Michael J; Kruger, Albert A; Doonan, Christian J; Thallapally, Praveen K

    2016-09-01

    The efficient removal of pertechnetate (TcO4(-)) anions from liquid waste or melter off-gas solution for an alternative treatment is one of the promising options to manage (99)Tc in legacy nuclear waste. Safe immobilization of (99)Tc is of major importance because of its long half-life (t1/2 = 2.13 × 10(5) yrs) and environmental mobility. Different types of inorganic and solid-state ion-exchange materials have been shown to absorb TcO4(-) anions from water. However, both high capacity and selectivity have yet to be achieved in a single material. Herein, we show that a protonated version of an ultrastable zirconium-based metal-organic framework can adsorb perrhenate (ReO4(-)) anions, a nonradioactive surrogate for TcO4(-), from water even in the presence of other common anions. Synchrotron-based powder X-ray diffraction and molecular simulations were used to identify the position of the adsorbed ReO4(-) (surrogate for TcO4(-)) molecule within the framework. PMID:27494264

  10. Rhenium volatilisation as caesium perrhenate from simulated vitrified high level waste from a melter crucible

    SciTech Connect

    Taylor, T.A.; Short, R.J.; Gribble, N.R.; Roe, J.I.; Steele, C.J.

    2013-07-01

    The Waste Vitrification Plant (WVP) converts Highly Active Liquor (HAL) from spent nuclear fuel reprocessing into a stable vitrified product. Recently WVP have been experiencing accumulation of solids in their primary off gas (POG) system leading to potential blockages. Chemical analysis of the blockage material via Laser Induced Breakdown Spectroscopy (LIBS) has shown it to exclusively consist of caesium, technetium and oxygen. The solids are understood to be caesium pertechnetate (CsTcO{sub 4}), resulting from the volatilisation of caesium and technetium from the high level waste glass melt. Using rhenium as a chemical surrogate for technetium, a series of full scale experiments have been performed in order to understand the mechanism of rhenium volatilisation as caesium perrhenate (CsReO{sub 4}), and therefore technetium volatilisation as CsTcO{sub 4}. These experiments explored the factors governing volatilisation rates from the melt, potential methods of minimising the amount of volatilisation, and various strategies for mitigating the deleterious effects of the volatile material on the POG. This paper presents the results from those experiments, and discusses potential methods to minimise blockages that can be implemented on WVP, so that the frequency of the CsTcO{sub 4} blockages can be reduced or even eradicated altogether. (authors)

  11. Perrhenate and Pertechnetate Behavior on Iron and Sulfur-Bearing Compounds

    SciTech Connect

    Anderson, B.E.; Becker, U.; Helean, K.B.; Ewing, R.C.

    2007-07-01

    Investigations of the behavior of the element {sup 99}Tc frequently use a stable isotope of rhenium as an analogue. This is based on the elements? similar radii, major oxidation states of +7 and +4, and analogous eH-pH diagrams. However, recent studies [1] have shown this analogy to be imperfect. Therefore, one goal of this study is to compare the behavior of these elements, with an emphasis on the adsorption of perrhenate and pertechnetate (the major forms of Re and Tc in natural waters) onto mineral surfaces. Quantum mechanical calculations were performed for the adsorption of these two anions onto relaxed clusters of the well-characterized sulfide galena (PbS). With these calculations, we have gained insight into differences between the anions adsorption behavior, including geometry, adsorption energies, and electronic structure. Differences between interactions on terraces and step edges, the effects of co-adsorbates such as Na{sup +} and Cl{sup -}, and chloride complexation were also explored. The influence of water was calculated using homogeneous dielectric fluids.As a complement to the calculations, batch sorption tests are in progress involving ReO{sub 4}{sup -}/TcO{sub 4}{sup -} solution in contact with Fe metal, 10% Fe-doped hydroxyapatite, goethite, hematite, magnetite, pyrite, galena, pyrrhotite, and sphalerite. (authors)

  12. Perrhenate and Pertechnetate Behavior on Iron and Sulfur-Bearing Compounds.

    SciTech Connect

    B.E. Anderson; U. Becker; K.B. Helean; R.C. Ewing

    2006-09-15

    Investigations on the behavior of the radioactive element technetium frequently use a stable isotope of rhenium as an analogue. This is justified by citing the elements similar radii and major oxidation states of +7 and +4. However, at least one study [1] has shown this analogy to be imperfect. Therefore, one goal of our study is to compare the adsorption behavior of perrhenate and pertechnetate (the major forms of Re and Tc in natural waters) on a number of different mineral surfaces. Quantum mechanical calculations were performed on the adsorption of these two anions on a series of iron oxides and sulfides. With these calculations, we gain insight into any differences between the anions adsorption behavior, including geometry, adsorption energies, and electronic structure such as density of states and orbital shapes and energies at the adsorption site. Differences between interactions on terraces and step edges, the effects of co-adsorbates such as Na{sup +} or H{sup +}, and possible reduction mechanisms are also explored. The influence of water was calculated using homogeneous dielectric fluids and explicit water molecules. As a complement to the calculations, batch sorption tests are in progress involving ReO{sub 4}{sup -}/TcO{sub 4}{sup -} solution in contact with Fe metal, 10% Fe-doped hydroxyapatite, goethite, hematite, magnetite, pyrite, galena, and sphalerite.

  13. 4-Methoxyanilinium Perrhenate 18-Crown-6: A New Ferroelectric with Order Originating in Swinglike Motion Slowing Down

    NASA Astrophysics Data System (ADS)

    Fu, Da-Wei; Cai, Hong-Ling; Li, Shen-Hui; Ye, Qiong; Zhou, Lei; Zhang, Wen; Zhang, Yi; Deng, Feng; Xiong, Ren-Gen

    2013-06-01

    A supramolecular adduct 4-methoxyanilinium perrhenate 18-crown-6 was synthesized, which undergoes a disorder-order structural phase transition at about 153 K (Tc) due to slowing down of a pendulumlike motion of the 4-methoxyanilinium group upon cooling. Ferroelectric hysteresis loop measurements give a spontaneous polarization of 1.2μC/cm2. Temperature-dependent solid-state nuclear magnetic resonance measurements reveal three kinds of molecular motions existing in the compound: pendulumlike swing of 4-methoxyanilinium cation, rotation of 18-crown-6 ring, and rotation of the methoxyl group. When the temperature decreases, the first two motions are frozen at about 153 K and the methoxyl group becomes rigid at around 126 K. The slowing down or freezing of pendulumlike motion of the cation triggered by temperature decreasing corresponds to the centrosymmetric-to-noncentrosymmetric arrangement of the compound, resulting in the formation of ferroelectricity.

  14. Experimental determination of the speciation, partitioning, and release of perrhenate as a chemical surrogate for pertechnetate from a sodalite-bearing multiphase ceramic waste form

    SciTech Connect

    Pierce, Eric M.; Lukens, Wayne W.; Fitts, Jeff. P.; Jantzen, Carol. M.; Tang, G.

    2013-12-01

    A key component to closing the nuclear fuel cycle is the storage and disposition of nuclear waste in geologic systems. Multiphase ceramic waste forms have been studied extensively as a potential host matrix for nuclear waste. Understanding the speciation, partitioning, and release behavior of radionuclides immobilized in multiphase ceramic waste forms is a critical aspect of developing the scientific and technical basis for nuclear waste management. In this study, we evaluated a sodalite-bearing multiphase ceramic waste form (i.e., fluidized-bed steam reform sodium aluminosilicate [FBSR NAS] product) as a potential host matrix for long-lived radionuclides, such as technetium (99Tc). The FBSR NAS material consists primarily of nepheline (ideally NaAlSiO4), anion-bearing sodalites (ideally M8[Al6Si6O24]X2, where M refers to alkali and alkaline earth cations and X refers to monovalent anions), and nosean (ideally Na8[AlSiO4]6SO4). Bulk X-ray absorption fine structure analysis of the multiphase ceramic waste form, suggest rhenium (Re) is in the Re(VII) oxidation state and has partitioned to a Re-bearing sodalite phase (most likely a perrhenate sodalite Na8[Al6Si6O24](ReO4)2). Rhenium was added as a chemical surrogate for 99Tc during the FBSR NAS synthesis process. The weathering behavior of the FBSR NAS material was evaluated under hydraulically unsaturated conditions with deionized water at 90 ?C. The steady-state Al, Na, and Si concentrations suggests the weathering mechanisms are consistent with what has been observed for other aluminosilicate minerals and include a combination of ion exchange, network hydrolysis, and the formation of an enriched-silica surface layer or phase. The steady-state S and Re concentrations are within an order of magnitude of the nosean and perrhenate sodalite solubility, respectively. The order of magnitude difference between the observed and predicted concentration for Re and S may be associated with the fact that the anion

  15. Experimental Determination of the Speciation, Partitioning, and Release of Perrhenate as a Chemical Surrogate for Pertechnetate from a Sodalite-Bearing Multiphase Ceramic Waste Form

    SciTech Connect

    Pierce, Eric M; Lukens, Wayne W; Fitts, Jeffrey P; Tang, Guoping; Jantzen, C M

    2013-01-01

    A key component to closing the nuclear fuel cycle is the storage and disposition of nuclear waste in geologic systems. Multiphase ceramic waste forms have been studied extensively as a potential host matrix for nuclear waste. Understanding the speciation, partitioning, and release behavior of radionuclides immobilized in multiphase ceramic waste forms is a critical aspect of developing the scientific and technical basis for nuclear waste management. In this study, we evaluated a sodalite-bearing multiphase ceramic waste form (i.e., fluidized-bed steam reform sodium aluminosilicate [FBSR NAS] product) as a potential host matrix for long-lived radionuclides, such as technetium (99Tc). The FBSR NAS material consists primarily of nepheline (ideally NaAlSiO4), anion-bearing sodalites (ideally M8[Al6Si6O24]X2, where M refers to alkali and alkaline earth cations and X refers to monovalent anions), and nosean (ideally Na8[AlSiO4]6SO4). Bulk x-ray absorption fine structure analysis of the multiphase ceramic waste form, suggest rhenium (Re) is in the Re(VII) oxidation state and has partitioned to a Re-bearing sodalite phase (most likely a perrhenate sodalite Na8[Al6Si6O24](ReO4)2). Rhenium was added as a chemical surrogate for 99Tc during the FBSR NAS synthesis process. The weathering behavior of the FBSR NAS material was evaluated under hydraulically unsaturated conditions with deionized water at 90 C. The steady-state Al, Na, and Si concentrations suggests the weathering mechanisms are consistent with what has been observed for other aluminosilicate minerals and include a combination of ion exchange, network hydrolysis, and the formation of an enriched-silica surface layer or phase. The steady-state S and Re concentrations are within an order of magnitude of the nosean and perrhenate sodalite solubility, respectively. The order of magnitude difference between the observed and predicted concentration for Re and S may be associated with the fact that the anion

  16. Pharmacokinetics of 99Tcm-pertechnetate and 188Re-perrhenate after oral administration of perchlorate: option for subsequent care after the use of liquid 188Re in a balloon catheter.

    PubMed

    Kotzerke, J; Fenchel, S; Guhlmann, A; Stabin, M; Rentschler, M; Knapp, F F; Reske, S N

    1998-08-01

    Radioactive wires and other linear sources are currently being used in clinical trials as endovascular brachytherapy to prevent restenosis after percutaneous transluminal coronary angioplasty. A new concept is the use of a liquid-filled balloon containing a beta-emitting radioisotope. A major advantage is optimal delivery of the radioactivity to the vessel wall. Rhenium-188 (188Re) is a high-energy beta-emitter that is routinely available from a 188W/188Re generator in liquid form. Since 188Re-perrhenate could be released in the unlikely event of balloon rupture, we investigated whether, in analogy to pertechnetate, subsequent use of perchlorate can reduce the uptake of perrhenate in the thyroid. We performed static (n = 9) and dynamic (n = 11) thyroid scintigraphy with 99Tcm-pertechnetate to estimate the overall reduction in activity within 30 min and the washout from the thyroid after oral administration of 600 mg perchlorate (T1/2). In two patients, 188Re was injected to estimate the whole-body distribution and the discharge of thyroid activity after perchlorate use. Based on MIRD Dose Estimate Report No. 8 (valid for 99Tcm-pertechnetate), the radiation burden was calculated for intravenous administration of 188Re and competitive blocking with perchlorate. In 20 patients, 99Tcm uptake by the thyroid was reduced by 85% within 30 min by perchlorate. The mean (+/- S.D.) washout rate (T1/2) was 8 +/- 2 min in 11 patients. Perrhenate showed a whole-body distribution similar to that of pertechnetate and the thyroid activity could be displaced (T1/2 = 6.3 and 9.3 min, respectively) by oral administration of perchlorate, with reductions in uptake of 83% and 75% within 30 min, respectively. Whole-body scanning demonstrated no regional accumulation of 188Re-perrhenate with excretion by urine. Dose estimates gave an effective dose equivalent of 0.42 mSv MBq-1, which decreased to 0.16 mSv MBq-1 after perchlorate blocking. 188Re has favourable properties for endovascular

  17. Solid-state (185/187)Re NMR and GIPAW DFT study of perrhenates and Re2(CO)10: chemical shift anisotropy, NMR crystallography, and a metal-metal bond.

    PubMed

    Widdifield, Cory M; Perras, Frédéric A; Bryce, David L

    2015-04-21

    Advances in solid-state nuclear magnetic resonance (SSNMR) methods, such as dynamic nuclear polarization (DNP), intricate pulse sequences, and increased applied magnetic fields, allow for the study of systems which even very recently would be impractical. However, SSNMR methods using certain quadrupolar probe nuclei (i.e., I > 1/2), such as (185/187)Re remain far from fully developed due to the exceedingly strong interaction between the quadrupole moment of these nuclei and local electric field gradients (EFGs). We present a detailed high-field (B0 = 21.1 T) experimental SSNMR study on several perrhenates (KReO4, AgReO4, Ca(ReO4)2·2H2O), as well as ReO3 and Re2(CO)10. We propose solid ReO3 as a new rhenium SSNMR chemical shift standard due to its reproducible and sharp (185/187)Re NMR resonances. We show that for KReO4, previously poorly understood high-order quadrupole-induced effects (HOQIE) on the satellite transitions can be used to measure the EFG tensor asymmetry (i.e., ηQ) to nearly an order-of-magnitude greater precision than competing SSNMR and nuclear quadrupole resonance (NQR) approaches. Samples of AgReO4 and Ca(ReO4)2·2H2O enable us to comment on the effects of counter-ions and hydration upon Re(vii) chemical shifts. Calcium-43 and (185/187)Re NMR tensor parameters allow us to conclude that two proposed crystal structures for Ca(ReO4)2·2H2O, which would be considered as distinct, are in fact the same structure. Study of Re2(CO)10 provides insights into the effects of Re-Re bonding on the rhenium NMR tensor parameters and rhenium oxidation state on the Re chemical shift value. As overtone NQR experiments allowed us to precisely measure the (185/187)Re EFG tensor of Re2(CO)10, we were able to measure rhenium chemical shift anisotropy (CSA) for the first time in a powdered sample. Experimental observations are supported by gauge-including projector augmented-wave (GIPAW) density functional theory (DFT) calculations, with NMR tensor calculations also

  18. Direct observation of ¹⁷O-¹⁸⁵/¹⁸⁷Re ¹J-coupling in perrhenates by solid-state ¹⁷O VT MAS NMR: temperature and self-decoupling effects.

    PubMed

    Jakobsen, Hans J; Bildsøe, Henrik; Brorson, Michael; Gan, Zhehong; Hung, Ivan

    2013-05-01

    (17)O MAS NMR spectra recorded at 14.1T and room temperature (RT) for (17)O-enriched samples of the two perrhenates, KReO4 and NH4ReO4, exhibit very similar overall appearances of the manifold of spinning sidebands (ssbs) for the satellite transitions (STs) and the central transition (CT). These overall appearances of the spectra are easily simulated in terms of the usual quadrupole coupling and chemical shift interaction parameters. However, a detailed inspection of the line shapes for the individual ssbs of the STs and, in particular, for the CT in the spectrum of KReO4 reveals line-shape features, which to our knowledge have not before been observed experimentally in 1D MAS NMR spectra for any quadrupolar nucleus, nor emerged from simulations for any combination of second-order quadrupolar interaction and chemical shift anisotropy. In contrast, such line-shape features are not observed for the corresponding ssbs (STs and CT) in the 14.1T RT (17)O MAS NMR spectrum of NH4ReO4. Considering the additional interaction of a combination of residual heteronuclear (17)O-(185/)(187)Re dipolar and scalar J coupling between this spin pair of two quadrupolar nuclei, spectral simulations for KReO4 show that these interactions are able to account for the observed line shapes, although the expected (1)J((17)O-(185/)(187)Re) six-line spin-spin splittings are not resolved. Low-temperature, high-field (21.1T) (17)O VT MAS NMR spectra of both KReO4 and NH4ReO4 show that full resolution into six-line multiplets for the centerbands are achieved at -90°C and -138°C, respectively. This allows determination of (1)J((17)O-(187)Re)=-268Hz and -278Hz for KReO4 and NH4ReO4, respectively, i.e., an isotropic (1)J coupling and its sign between two quadrupolar nuclei, observed for the first time directly from solid-state one-pulse 1D MAS NMR spectra, without resort to additional 1D or 2D experiments. Determination of T1((187)Re) spin-lattice relaxation times, observed indirectly through a 2D

  19. Concentration of perrhenate and pertechnetate solutions

    DOEpatents

    Knapp, F.F.; Beets, A.L.; Mirzadeh, S.; Guhlke, S.

    1998-03-17

    A method is described for preparing a concentrated solution of a carrier-free radioisotope which includes the steps of: (a) providing a generator column loaded with a composition containing a parent radioisotope; (b) eluting the generator column with an eluent solution which includes a salt of a weak acid to elute a target daughter radioisotope from the generator column in a first eluate; (c) eluting a cation-exchange column with the first eluate to exchange cations of the salt for hydrogen ions and to elute the target daughter radioisotope and a weak acid in a second eluate; (d) eluting an anion-exchange column with the second eluate to trap and concentrate the target daughter radioisotope and to elute the weak acid solution therefrom; and (e) eluting the concentrated target daughter radioisotope from the anion-exchange column with a saline solution. 1 fig.

  20. Concentration of perrhenate and pertechnetate solutions

    SciTech Connect

    Knapp, Furn F.; Beets, Arnold L.; Mirzadeh, Saed; Guhlke, Stefan

    1998-01-01

    A method of preparing a concentrated solution of a carrier-free radioisotope which includes the steps of: a. providing a generator column loaded with a composition containing a parent radioisotope; b. eluting the generator column with an eluent solution which includes a salt of a weak acid to elute a target daughter radioisotope from the generator column in a first eluate. c. eluting a cation-exchange column with the first eluate to exchange cations of the salt for hydrogen ions and to elute the target daughter radioisotope and a weak acid in a second eluate; d. eluting an anion-exchange column with the second eluate to trap and concentrate the target daughter radioisotope and to elute the weak acid solution therefrom; and e. eluting the concentrated target daughter radioisotope from the anion-exchange column with a saline solution.

  1. Tungsten-188/carrier-free rhenium-188 perrhenic acid generator system

    DOEpatents

    Knapp, Jr., Furn F.; Lisic, Edward C.; Mirzadeh, Saed; Callahan, Alvin P.

    1994-01-01

    A generator system for providing a carrier-free radioisotope in the form of an acid comprises a chromatography column in tandem fluid connection with an ion exchange column, the chromatography column containing a charge of a radioactive parent isotope. The chromatography column, charged with a parent isotope, is eluted with an alkali metal salt solution to generate the radioisotope in the form of an intermediate solution, which is passed through the ion-exchange column to convert the radioisotope to a carrier-free acid form.

  2. Tungsten-188/carrier-free rhenium-188 perrhenic acid generator system

    DOEpatents

    Knapp, Jr., Furn F.; Lisic, Edward C.; Mirzadeh, Saed; Callahan, Alvin P.

    1993-01-01

    A generator system for providing a carrier-free radioisotope in the form of an acid comprises a chromatography column in tandem fluid connection with an ion exchange column, the chromatography column containing a charge of a radioactive parent isotope. The chromatography column, charged with a parent isotope, is eluted with an alkali metal salt solution to generate the radioisotope in the form of an intermediate solution, which is passed through the ion-exchange column to convert the radioisotope to a carrier-free acid form.

  3. Tungsten-188/carrier-free rhenium-188 perrhenic acid generator system

    DOEpatents

    Knapp, F.F. Jr.; Lisic, E.C.; Mirzadeh, S.; Callahan, A.P.

    1993-02-16

    A generator system for providing a carrier-free radioisotope in the form of an acid comprises a chromatography column in tandem fluid connection with an ion exchange column, the chromatography column containing a charge of a radioactive parent isotope. The chromatography column, charged with a parent isotope, is eluted with an alkali metal salt solution to generate the radioisotope in the form of an intermediate solution, which is passed through the ion-exchange column to convert the radioisotope to a carrier-free acid form.

  4. Tungsten-188/carrier-free rhenium-188 perrhenic acid generator system

    DOEpatents

    Knapp, F.F. Jr.; Lisic, E.C.; Mirzadeh, S.; Callahan, A.P.

    1994-01-04

    A generator system has been invented for providing a carrier-free radioisotope in the form of an acid comprises a chromatography column in tandem fluid connection with an ion exchange column, the chromatography column containing a charge of a radioactive parent isotope. The chromatography column, charged with a parent isotope, is eluted with an alkali metal salt solution to generate the radioisotope in the form of an intermediate solution, which is passed through the ion-exchange column to convert the radioisotope to a carrier-free acid form. 1 figure.

  5. Crystal structure of the high-temperature modification of ytterbium perrhenate Yb(ReO{sub 4}){sub 3}

    SciTech Connect

    Khrustalev, V.N.; Varfolomeev, M.B.; Shamrai, N.B.; Struchkov, Yu.T.; Pisarevskii, A.P. |

    1993-11-01

    Yb(ReO{sub 4}){sub 3} obtained by the slow crystallization of its melt in air is investigated by X-ray diffraction (298 K, 329 reflections, R = 0.083, R{sub w} = 0.102). Crystals are hexagonal, a = 9.999(4) {angstrom}, c = 6.070(2) {angstrom}, Z = 2, space group P6{sub 3}/m. The structure is related to the CdTh(MoO{sub 4}){sub 3} type and consists of columns of Yb polyhedra (three-cap trigonal prisms) and of Re tetrahedra. The correlation of the structures of Yb(ReO{sub 4}){sub 3} and apatite is discussed.

  6. Copper(II) perrhenate Cu(C3H7OH)2(ReO4)2: Synthesis from isopropanol and CuReO4, structure and properties

    NASA Astrophysics Data System (ADS)

    Mikhailova, D.; Engel, J. M.; Schmidt, M.; Tsirlin, A. A.; Ehrenberg, H.

    2015-12-01

    The crystal structure of Cu+Re7+O4 is capable of a quasi-reversible incorporation of C3H7OH molecules. A room-temperature reaction between CuReO4 and C3H7OH under oxidizing conditions leads to the formation of a novel metal-organic hybrid compound Cu2+(C3H7OH)2(ReO4)2. Upon heating under reducing conditions, this compound transforms back into CuReO4, albeit with ReO2 and metallic Cu as by-products. The crystal structure of Cu(C3H7OH)2(ReO4)2 solved from single-crystal X-ray diffraction (Pbca, a=10.005(3) Å, b=7.833(2) Å, and c=19.180(5) Å) reveals layers of corner-sharing CuO6-octahedra and ReO4-tetrahedra, whereas isopropyl groups are attached to both sides of these layers, thus providing additional connections within the layers through hydrogen bonds. Cu(C3H7OH)2(ReO4)2 is paramagnetic down to 4 K because the spatial arrangement of the Cu2+ half-filled orbitals prevents magnetic superexchange. The paramagnetic effective moment of 2.0(1) μB is slightly above the spin-only value and typical for Cu2+ ions.

  7. Experimental Ion Exchange Column With SuperLig 639 And Simulant Formulation

    SciTech Connect

    Morse, Megan; Nash, C.

    2013-08-26

    SuperLig®639 ion exchange resin was tested as a retrieval mechanism for pertechnetate, through decontamination of a perrhenate spiked 5M Simple Average Na{sup +} Mass Based Simulant. Testing included batch contacts and a three-column ion exchange campaign. A decontamination of perrhenate exceeding 99% from the liquid feed was demonstrated. Analysis of the first formulation of a SBS/WESP simulant found unexpectedly low concentrations of soluble aluminum. Follow-on work will complete the formulation.

  8. Binding of ReO4(-) with an engineered MoO4(2-)-binding protein: towards a new approach in radiopharmaceutical applications.

    PubMed

    Aryal, Baikuntha P; Brugarolas, Pedro; He, Chuan

    2012-01-01

    Radiolabeled biomolecules are routinely used for clinical diagnostics. (99m)Tc is the most commonly used radioactive tracer in radiopharmaceuticals. (188)Re and (186)Re are also commonly used as radioactive tracers in medicine. However, currently available methods for radiolabeling are lengthy and involve several steps in bioconjugation processes. In this work we present a strategy to engineer proteins that may selectively recognize the perrhenate (ReO(4)(-)) ion as a new way to label proteins. We found that a molybdate (MoO(4)(2-))-binding protein (ModA) from Escherichia coli can bind perrhenate with high affinity. Using fluorescence and isothermal titration calorimetry measurements, we determined the dissociation constant of ModA for ReO(4)(-) to be 541 nM and we solved a crystal structure of ModA with a bound ReO(4)(-). On the basis of the structure we created a mutant protein containing a disulfide linkage, which exhibited increased affinity for perrhenate (K(d) = 104 nM). High-resolution crystal structures of ModA (1.7 Å) and A11C/R153C mutant (2.0 Å) were solved with bound perrhenate. Both structures show that a perrhenate ion occupies the molybdate binding site using the same amino acid residues that are involved in molybdate binding. The overall structure of the perrhenate-bound ModA is unchanged compared with that of the molybdate-bound form. In the mutant protein, the bound perrhenate is further stabilized by the engineered disulfide bond. PMID:21861186

  9. Binding of ReO[subscript 4];#8722; with an engineered MoO[subscript 4 superscript 2];#8722;-binding protein: towards a new approach in radiopharmaceutical applications

    SciTech Connect

    Aryal, Baikuntha P.; Brugarolas, Pedro; He, Chuan

    2012-05-25

    Radiolabeled biomolecules are routinely used for clinical diagnostics. {sup 99m}Tc is the most commonly used radioactive tracer in radiopharmaceuticals. {sup 188}Re and {sup 186}Re are also commonly used as radioactive tracers in medicine. However, currently available methods for radiolabeling are lengthy and involve several steps in bioconjugation processes. In this work we present a strategy to engineer proteins that may selectively recognize the perrhenate (ReO{sub 4}{sup -}) ion as a new way to label proteins. We found that a molybdate (MoO{sub 4}{sup 2-})-binding protein (ModA) from Escherichia coli can bind perrhenate with high affinity. Using fluorescence and isothermal titration calorimetry measurements, we determined the dissociation constant of ModA for ReO{sub 4}{sup -} to be 541 nM and we solved a crystal structure of ModA with a bound ReO{sub 4}{sup -}. On the basis of the structure we created a mutant protein containing a disulfide linkage, which exhibited increased affinity for perrhenate (K{sub d} = 104 nM). High-resolution crystal structures of ModA (1.7 {angstrom}) and A11C/R153C mutant (2.0 {angstrom}) were solved with bound perrhenate. Both structures show that a perrhenate ion occupies the molybdate binding site using the same amino acid residues that are involved in molybdate binding. The overall structure of the perrhenate-bound ModA is unchanged compared with that of the molybdate-bound form. In the mutant protein, the bound perrhenate is further stabilized by the engineered disulfide bond.

  10. Elution of Re-188 from W-188/Re-188 generators with salts of weak acids permits efficient concentration to low volumes using a new tandem cation/anion exchange system

    SciTech Connect

    Guhlke, S. |; Beets, A.L.; Knapp, F.F. Jr.

    1997-05-01

    Re-188, available from a W-188/Re-188 generator, is an important therapeutic radioisotope for bone pain palliation, cancer therapy and intravascular brachytherapy, etc. Because of the relatively low specific activity of reactor-produced W-188 (ORNL HFIR, 296-370 MBq mCi/mg W-186 for 2 cycles), methods of concentrating the Re-188 bolus (10-12 mL) from clinical scale (18.5-37 BGq W-188) generators (5-6 gm alumina) are thus very important. We demonstrate for the first time a new strategy of generator elution with salts of weak acids and specific perrhenate anion {open_quotes}trapping{close_quotes} with QMA anion columns. Re-188 perrhenate is efficiently eluted (65-75%) from the alumina-based generator with 0.15-0.3 M ammonium acetate. An acetic acid solution of Re-188 perrhenic acid is obtained by subsequent on-line passage of the generator eluant through a DOWEX AG 50Wx8 (200-400 mesh, H{sup +} form) column. Since acetic acid is not ionized (< 0.001%) at this pH (< pK{sub a} = 4.76) the perrhenate anion is then specifically trapped on a QMA {open_quotes}Light{close_quotes} anion extraction column. QMA elution with 0.9% NaCl, provides Re-188 perrhenate solution in <1 mL. Concentration of 10-20 mL of Re-188 solution (> 15 BGq) in <1 mL has been demonstrated using this simple new approach, which is also effective for concentration of Tc-99m from low specific activity Mo-99 (n,y) generators. The cation/anion tandem system is inexpensive and disposable and use can be easily automated. The availability of this very simple, efficient system is important for broad use of rhenium-188.

  11. Olefin Epoxidation in Aqueous Phase Using Ionic-Liquid Catalysts.

    PubMed

    Cokoja, Mirza; Reich, Robert M; Wilhelm, Michael E; Kaposi, Marlene; Schäffer, Johannes; Morris, Danny S; Münchmeyer, Christian J; Anthofer, Michael H; Markovits, Iulius I E; Kühn, Fritz E; Herrmann, Wolfgang A; Jess, Andreas; Love, Jason B

    2016-07-21

    Hydrophobic imidazolium-based ionic liquids (IL) act as catalysts for the epoxidation of unfunctionalized olefins in water using hydrogen peroxide as oxidant. Although the catalysts are insoluble in both the substrate and in water, surprisingly, they are very well soluble in aqueous H2 O2 solution, owing to perrhenate-H2 O2 interactions. Even more remarkably, the presence of the catalyst also boosts the solubility of substrate in water. This effect is crucially dependent on the cation design. Hence, the imidazolium perrhenates enable both the transfer of hydrophobic substrate into the aqueous phase, and serve as actual catalysts, which is unprecedented. At the end of the reaction and in absence of H2 O2 the IL catalyst forms a third phase next to the lipophilic product and water and can easily be recycled. PMID:27219852

  12. Novel and efficient preparation of precursor [188Re(OH2)3(CO)3]+ for the labeling of biomolecules.

    PubMed

    Park, Sang Hyun; Seifert, Sepp; Pietzsch, Hans-Jurgen

    2006-01-01

    A novel and efficient method for preparing 188Re(I) tricarbonyl precursor [188Re(OH2)3(CO)3]+ has been developed by reacting [188Re]perrhenate with Schibli's kit in the presence of borohydride exchange resin (BER) as a reducing agent and an anion scavenger. The precursor was produced in more than 97% yield by reacting a solution of tetrahydroborate exchange resin (BER, 3 mg), borane-ammonia (BH3.NH3, 3 mg), and potassium boranocarbonate (K2[H3BCO2], 3 mg) in 0.9% saline with a solution of sodium perrhenate (Na188ReO4) with up to 50 MBq and concentrated phosphoric acid (85%, 7 microL) at 60 degrees C for 15 min. HPLC and TLC revealed 0% unreacted [188Re]perrhenate ion and <3% of colloidal 188ReO2. Since the precursor is produced with high radiochemical purity and labeling efficiency under the milder conditions than those required for the conventional reducing agents, the latter can be replaced. PMID:16417272

  13. Rhenium-188--a generator-derived radioisotope for cancer therapy.

    PubMed

    Knapp, F F

    1998-10-01

    Rhenium-188 (188Re) is an important therapeutic radioisotope which is obtained on demand as carrier-free sodium perrhenate by saline elution of the tungsten-188/rhenium-188 generator system. With a half-life of 16.9 hours and emission of a high energy beta particle (maximal energy of 2.12 MeV) and a gamma photon (155 keV, 15%) for imaging, 188Re can be provided at reasonable costs for routine preparation of radiopharmaceuticals for cancer treatment. PMID:10851424

  14. New Gel-Like Polymers as Selective Weak-Base Anion Exchangers

    PubMed Central

    Gierczyk, Błażej; Cegłowski, Michał; Zalas, Maciej

    2015-01-01

    A group of new anion exchangers, based on polyamine podands and of excellent ion-binding capacity, were synthesized. The materials were obtained in reactions between various poly(ethyleneamines) with glycidyl derivatives of cyclotetrasiloxane. The final polymeric, strongly cross-linked materials form gel-like solids. Their structures and interactions with anions adsorbed were studied by spectroscopic methods (CP-MAS NMR, FR-IR, UV-Vis). The sorption isotherms and kinetic parameters were determined for 29 anions. Materials studied show high ion capacity and selectivity towards some important anions, e.g., selenate(VI) or perrhenate. PMID:25946220

  15. Purification of alkaline solutions and wastes from actinides and technetium by coprecipitation with some carriers using the method of appearing reagents: Final Report

    SciTech Connect

    Peretrukhin, V.F.; Silin, V.I.; Kareta, A.V.; Gelis, A.V.; Shilov, V.P.; German, K.E.; Firsova, E.V.; Maslennikov, A.G.; Trushina, V.E.

    1998-09-01

    The coprecipitation of transuranium elements (TRU) and technetium from alkaline solutions and from simulants of Hanford Site tank wastes has been studied in reducing and oxidizing conditions on uranium(IV,VI) hydroxocompounds, tetraalkylammonium perrhenate and perchlorate, and on hydroxides of Fe(III), Co(III), Mn(II), and Cr(III) using the method of appearing reagents (MAR). Coprecipitations in alkaline solution have been shown to give high decontamination factors (DF) at low content of carrier and in the presence of high salt concentrations. Uranium(IV) hydroxide in concentrations higher than 3 {times} 10{sup {minus}3} M coprecipitates Pu and Cm in any oxidation state from 0.2 to 4 M NaOH with DFs of 110 to 1000 and Np and Tc with DFs of 51 to 176. Technetium (VII) coprecipitates with (5 to 8) {times} 10{sup {minus}4} M tetrabutylammonium (TBA) perrhenate in 0.01 to 0.02 M TBA hydroxide from 0.5 to 1.5 M NaOH to give DFs of 150 to 200. Coprecipitations of Np and Pu with Co(OH){sub 3}, Fe(OH){sub 3}, Cr(OH){sub 3}, and Mn(OH){sub 2} obtained by the MAR from precursors in the range from pH 10.5 to 0.4 M NaOH give DFs from 80 to 400.

  16. Study of the structure of PyHReO{sub 4} under high pressure

    SciTech Connect

    Kichanov, S. E. Kozlenko, D. P.; Wasicki, J. W.; Czarnecki, P.; Glazkov, V. P.; Nawrocik, W.; Savenko, B. N.; Lathe, C.

    2007-05-15

    The structure of deuterated pyridinium perrhenate (d{sub 5}PyH)ReO{sub 4} (C{sub 5}D{sub 5}NHReO{sub 4}) is studied by X-ray diffraction at room temperature and pressures up to 3.5 GPa and by neutron diffraction in the temperature range 10-293 K and at pressures up to 2.0 GPa. Under normal conditions, this compound belongs to the orthorhombic space group Cmc2{sub 1} (ferroelectric phase II). At room temperature and pressures above P > 0.7 GPa, a transition to an orthorhombic phase (paraelectric phase II) is observed. This paraelectric phase is described by the space group Cmcm. At a pressure as high as P = 2.0 GPa, phase I remains stable at temperatures down to 10 K. This fact indicates that the high pressure suppresses the ferroelectric state in deuterated pyridinium perrhenate (d{sub 5}PyH)ReO{sub 4}.

  17. Intraarterial irradiation with rhenium-188 for inhibition of restenosis after PTCA - strategy and evaluation of Re-188-species for rapid urinary excretion

    SciTech Connect

    Knapp, F.F. Jr.; Guhlke, S.; Beets, A.L.

    1997-05-01

    Estimated costs for coronary restenosis therapy after PTCA are > $ 1 billion (U.S.). Radiation is a simple and effective tool for inhibition of neointimal proliferation an important component of restenosis. We propose use of Re-188 (t{sub {1/2}} 16.9 h, 2.1 MeV {beta}), obtained from decay of W-188 (T{sub {1/2}} 69 d). Our alumina-based W-188/Re-188 generator has a shelf-life of several months and we have developed an on-line tandem cation/anion exchange column system to concentrate to > 18.5 BGq/mL. Estimates for targeted regional dose of 8.4 rad/37 MBq/min/mL, which is > 1,400 cGy for about 370 MBq Re-188 for 5 min. Balloon inflation with Re-188 solutions is a new approach for more uniform vascular dose distribution as an alternative to use of radioactive wires or other linear sources. Rapid urinary excretion kinetics are important in the unlikely event of balloon rupture (<0.1%). We have therefore evaluated relative excretion kinetics of Re-188-perrhenate and -MAG3 in rats; Re-188-perrhenate was obtained from generator elution with 0.9% NaCl and re-188-MAG3 was prepared be reaction of the ligand with Sn(II)-reduced perrhenate. Fischer rats (n=4-5/group) were injected i.v. and urine and feces collected every 2 h for 12 h and then daily for 5 d. Both agents excreted > 90% in urine; biodistribution studies showed low organ uptake with intestines as the major site. Rhenium-188-MAG3 excreted more rapidly (2 h = 59.6{+-}18.5%) then Re-188-MAG3 excreted more rapidly (2 h = 68.3{+-}13.5%) in same model. Both Re-188 species are thus good candidates for balloon inflation. Studies are in progress in a swine model to evaluate the effectiveness of Re-188 for inhibition of restenosis.

  18. Crystallization and rhenium MAD phasing of the acyl-homoserinelactone synthase EsaI.

    PubMed

    Watson, W T; Murphy, F V; Gould, T A; Jambeck, P; Val, D L; Cronan, J E; Beck von Bodman, S; Churchill, M E

    2001-12-01

    Acyl-homoserine-L-lactones (AHLs) are diffusible chemical signals that are required for virulence of many Gram-negative bacteria. AHLs are produced by AHL synthases from two substrates, S-adenosyl-L-methionine and acyl-acyl carrier protein. The AHL synthase EsaI, which is homologous to the AHL synthases from other pathogenic bacterial species, has been crystallized in the primitive tetragonal space group P4(3), with unit-cell parameters a = b = 66.40, c = 47.33 A. The structure was solved by multiple-wavelength anomalous diffraction with a novel use of the rhenium anomalous signal. The rhenium-containing structure has been refined to a resolution of 2.5 A and the perrhenate ion binding sites and liganding residues have been identified. PMID:11717525

  19. Methods for the separation of rhenium, osmium and molybdenum applicable to isotope geochemistry

    USGS Publications Warehouse

    Morgan, J.W.; Golightly, D.W.; Dorrzapf, A.F., Jr.

    1991-01-01

    Effective methods are described for the chemical separation of rhenium, osmium and molybdenum. The methods are based on distillation and anion-exchange chromatography, and have been the basis for rhenium-osmium isotope studies of ore deposits and meteorites. Successful anion-exchange separation of osmium requires both recognition and careful control of the osmium species in solution; thus, distillation of osmium tetroxide from a mixture of sulfuric acid and hydrogen peroxide is preferred to anion-exchange. Distribution coefficients measured for perrhenate in sulfuric acid media are sufficiently high (Kd > 500) for rhenium to be directly loaded onto an ion-exchange column from a distillation residue and subsequently eluted with nitric acid. Polymerization of molybdenum species during elution is prevented by use of a solution that is 1M in hydrochloric acid and 1M in sodium chloride. ?? 1991.

  20. Excited states of ReO4-: A comprehensive time-dependent relativistic density functional theory study

    NASA Astrophysics Data System (ADS)

    Xu, Wenhua; Ma, Jianyi; Peng, Daoling; Zou, Wenli; Liu, Wenjian; Staemmler, Volker

    2009-02-01

    The perrhenate anion, ReO4-, is taken as a showcase of heavy transition metal complexes, to examine the performance of time-dependent relativistic density functional linear response theory for electronic excitations, which is based on a newly proposed exact two-component Hamiltonian resulting from the symmetrized elimination of the small component. In total 30 scalar and 63 spinor excited states are investigated and the results are grossly in good agreement with those by the singles and doubles coupled-cluster linear response theory. It is found that only a few scalar states of 3T1 and 3T2 symmetries are split significantly by the spin-orbit coupling, whereas only those excited states involving the Rydberg-type virtual orbital are affected by the solvent effects. The nature of the optical absorption spectra is also highlighted.

  1. Crystallization and rhenium MAD phasing of the acyl-homoserinelactone synthase EsaI

    SciTech Connect

    Watson, W.T.; Murphy IV, Frank V.; Gould, Ty A.; Jambeck, Per; Val, Dale L.; Cronan, Jr., John E.; Beck von Bodman, Susan; Churchill, Mair E.A.

    2009-04-22

    Acyl-homoserine-L-lactones (AHLs) are diffusible chemical signals that are required for virulence of many Gram-negative bacteria. AHLs are produced by AHL synthases from two substrates, S-adenosyl-L-methionine and acyl-acyl carrier protein. The AHL synthase EsaI, which is homologous to the AHL synthases from other pathogenic bacterial species, has been crystallized in the primitive tetragonal space group P4{sub 3}, with unit-cell parameters a = b = 66.40, c = 47.33 {angstrom}. The structure was solved by multiple-wavelength anomalous diffraction with a novel use of the rhenium anomalous signal. The rhenium-containing structure has been refined to a resolution of 2.5 {angstrom} and the perrhenate ion binding sites and liganding residues have been identified.

  2. Energy harvesting from nanofibers of hybrid organic ferroelectric dabcoHReO4

    NASA Astrophysics Data System (ADS)

    Isakov, D.; de Matos Gomes, E.; Almeida, B.; Kholkin, A. L.; Zelenovskiy, P.; Neradovskiy, M.; Shur, V. Ya.

    2014-01-01

    We report excellent piezoelectric and pyroelectric properties of electrospun nanofibers based on the hybrid ferroelectric 1,4-diazabicyclo[2.2.2]octane perrhenate (dabcoHReO4). Ferroelectric nanoparticles are embedded into the fibers being naturally aligned with the major polarization component along the fiber axis. A flexible piezoelectric nanogenerator consisting of an aligned array of dabcoHReO4 fibers provides a voltage above 100 mV under a moderate strain level. The pyroelectric coefficient in as-electrospun dabcoHReO4 fiber mat is similar to that in poled polyvinylidene difluoride nanofibers. The results show that the nanofibers based on dabcoHReO4 have a great potential for pyroelectric and piezoelectric autonomous energy harvesting with natural advantages such as biocompatibility, flexibility, low cost, and easy fabrication.

  3. The Beta Environmental Fine Structure (BEFS): The XAFS Nuclear Analogue

    SciTech Connect

    Monfardini, A.; Benedek, G.; Cremonesi, O.; Nucciotti, A.; Sisti, M.; Filipponi, A.

    2007-02-02

    The Beta Environmental Fine Structure (BEFS) effect is an oscillatory modulation on the otherwise smooth spectrum of electrons emitted by beta-decaying nuclei. The existence of this effect was theoretically proposed in 1991, for condensed emitters, in analogy with XAFS. In BEFS the electron, playing the role of the XAFS photoelectron, originates directly from the nucleus and an anti-neutrino is emitted at the same time. We present evidence for BEFS oscillations observed in Silver Perrhenate (AgReO4) low-temperature (0.1K) microbolometers, together with a XAFS-like analysis that allowed for the first time a direct measurement of the anti-neutrino angular momentum. We discuss the physical analogies and differences between BEFS and XAFS and the implications for the next generation experiments aimed at measuring the neutrino mass on purely kinematic grounds. Moreover, we briefly discuss the potential and the limits of BEFS-based techniques with respect to the classical XAFS.

  4. Aqueous biphasic systems for metal separations : a microcalorimetric analysis of polymer/salt interactions.

    SciTech Connect

    Chaiko, D. J.; Hatton, T. A.; Zaslavsky, B.

    1999-05-03

    Certain radionuclide ions (e.g., TcO{sub 4}{sup 16}) exhibit unusually strong Affinities toward the polymer-rich phase in aqueous biphase systems generated by combinations of salt solutions with polymers such as poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG). Thus, aqueous polymer phases could potentially be used to selectively extract these ions during pretreatment of radioactive tank wastes at Hanford. To help develop a fundamental understanding of the interactions between various ions and polymers in aqueous solution, interaction enthalpies between sodium perrhenate and a random copolymer of PEG and PPG (UCON-50) were measured by microcalorimetric titration. An entropy compensation effect was observed in this system in which changes in enthalpic interactions were balanced by entropy changes such that the interaction free energy remained constant and approximately equal to zero.

  5. Microtitration of various anions with quaternary ammonium halides using solid-state electrodes

    SciTech Connect

    Selig, W.

    1980-01-01

    Many solid-state electrodes were found to respond as endpoint detectors in the potentiometric titration of large inorganic and organic anions with quaternary ammonium halides. The best response was obtained with the iodide and cyanide electrodes although practically any electrode can function as endpoint sensor. The titrants were hexadecylpyridinium chloride and hexadecyltrimethylammonium chloride; hexadecyltrimethylammonium bromide and Hyamine 1622 may also be used. Some inorganic anions thus titratable are perrhenate, persulfate, ferricyanide, hexafluorophosphate, and hexachloroplatinate. Examples of organic anions titratable are nitroform, tetraphenylborate, cyanotriphenylborate, picrate, long-chain sulfates and sulfonates, and some soaps. The reverse titration of quaternary ammonium halides vs dodecylsulfate is also feasible. Some titrations are feasible in a partially nonaqueous medium.

  6. 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

    2016-07-01

    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. PMID:27310580

  7. Studies of supported hydrodesulfurization catalysts: Progress report for September 1, 1987 to December 31, 1988

    SciTech Connect

    Hercules, D.M.

    1988-10-01

    The objectives of the proposal are: (1) to study the mechanism of adsorption of anions pertinent to HDS catalysts (Mo,W) on Al2O3 (or TiO2) surfaces, (2) to determine the distribution of Mo (or W) oxidation states in Mo (or W)/TiO2 (or Al2O3) catalysts on reduction and to correlate Mo oxidation state to the catalytic activity observed for various probe reactions, (3) to apply the methodology for quantitative analysis of the distribution of supported species by Laser Raman Spectroscopy (LRS) (developed from an early study of Mo/TiO2 catalysts) to other systems relevant to HDS catalysts (e.g., W/TiO2), and finally (4) to correlate the Mo (or W) speciation derived from LRS with HDS activity. The accomplishments of the past year are as follows: We have investigated the nature of the interaction of molybdate and tungstate with alumina by comparing their adsorption behavior with that of perrhenate and permanganate anions; We have monitored by ESCA and gravimetric analysis the changes in Mo oxidation states for Mo/TiO2 catalyst as a function of reduction conditions. The results were correlated with benzene hydrogenation activity. We have extended the methodology for quantitative analysis of the distribution of supported species by LRS to the W/TiO2 system. Finally, we have correlated the Mo speciation in Mo/TiO2 derived from LRS with HDS activity.

  8. Upgrade to Ion Exchange Modeling for Removal of Technetium from Hanford Waste Using SuperLig® 639 Resin

    SciTech Connect

    Hamm, L.; Smith, F.; Aleman, S.; McCabe, D.

    2013-05-16

    This report documents the development and application of computer models to describe the sorption of pertechnetate [TcO₄⁻], and its surrogate perrhenate [ReO₄⁻], on SuperLig® 639 resin. Two models have been developed: 1) A thermodynamic isotherm model, based on experimental data, that predicts [TcO₄⁻] and [ReO₄⁻] sorption as a function of solution composition and temperature and 2) A column model that uses the isotherm calculated by the first model to simulate the performance of a full-scale sorption process. The isotherm model provides a synthesis of experimental data collected from many different sources to give a best estimate prediction of the behavior of the pertechnetate-SuperLig® 639 system and an estimate of the uncertainty in this prediction. The column model provides a prediction of the expected performance of the plant process by determining the volume of waste solution that can be processed based on process design parameters such as column size, flow rate and resin physical properties.

  9. Tc and Re Behavior in Borosilicate Waste Glass Vapor Hydration Tests

    SciTech Connect

    McKeown, David A.; Buechele, Andrew C.; Pegg, Ian L.; Lukens, Wayne W.; Shuh, David K.

    2007-07-01

    Technetium (Tc), found in some nuclear wastes, is of particular concern with regard to long-term storage, because of its long-lived radioactivity and high mobility in the environment. Tc and rhenium (Re), commonly used as a non-radioactive surrogate for Tc, were studied to assess their behavior in borosilicate glass under hydrothermal conditions in the Vapor Hydration Test (VHT). X-ray absorption spectroscopy (XAS) and scanning electron microscopy (SEM) measurements were made on the original Tc- and Re-containing glasses and their corresponding VHT samples, and show different behavior for Tc and Re under VHT conditions. XAS indicates that, despite starting with different Tc(IV) and Tc(VII) distributions in each glass, the VHT samples have 100% Tc(IV)O{sub 6} environments. SEM shows complete alteration of the original glass, Tc enrichment near the sample surface, and Tc depletion in the center. Perrhenate (Re(VII)O{sub 4}{sup -}) is dominant in both Re-containing samples before and after the VHT, where Re is depleted near the VHT sample surface and more concentrated toward the center. (authors)

  10. Anion inhibition studies of the β-carbonic anhydrase from the pathogenic bacterium Vibrio cholerae.

    PubMed

    Vullo, Daniela; Del Prete, Sonia; De Luca, Viviana; Carginale, Vincenzo; Ferraroni, Marta; Dedeoglu, Nurcan; Osman, Sameh M; AlOthman, Zeid; Capasso, Clemente; Supuran, Claudiu T

    2016-03-01

    The genome of the pathogenic bacterium Vibrio cholerae encodes for three carbonic anhydrases (CAs, EC 4.2.1.1) belonging to the α-, β- and γ-classes. Here we report and anion inhibition study of the β-CA, VchCAβ with anions and other small molecules which inhibit metalloenzymes. The best VchCAβ anion inhibitors were sulfamide, sulfamate, phenylboronic acid and phenylarsonic acid, which showed KIs in the range of 54-86μM. Diethyldithiocarbonate was also an effective VchCAβ inhibitor, with an inhibition constant of 0.73mM. The halides, cyanate, thiocyanate, cyanide, bicarbonate, carbonate, nitrate, nitrite, stannate, selenate, tellurate, divanadate, tetraborate, perrhenate, perruthenate, peroxydisulfate, selenocyanide, trithiocarbonate, and fluorosulfonate showed affinity in the low millimolar range, with KIs of 2.3-9.5mM. Identification of selective inhibitors of VchCAβ (over the human CA isoforms) may lead to pharmacological tools useful for understanding the physiological role(s) of this under-investigated enzyme. PMID:26853167

  11. Rhenium solubility in borosilicate nuclear waste glass: implications for the processing and immobilization of technetium-99.

    PubMed

    McCloy, John S; Riley, Brian J; Goel, Ashutosh; Liezers, Martin; Schweiger, Michael J; Rodriguez, Carmen P; Hrma, Pavel; Kim, Dong-Sang; Lukens, Wayne W; Kruger, Albert A

    2012-11-20

    The immobilization of technetium-99 ((99)Tc) in a suitable host matrix has proven to be a challenging task for researchers in the nuclear waste community around the world. In this context, the present work reports on the solubility and retention of rhenium, a nonradioactive surrogate for (99)Tc, in a sodium borosilicate glass. Glasses containing target Re concentrations from 0 to 10,000 ppm [by mass, added as KReO(4) (Re(7+))] were synthesized in vacuum-sealed quartz ampules to minimize the loss of Re from volatilization during melting at 1000 °C. The rhenium was found as Re(7+) in all of the glasses as observed by X-ray absorption near-edge structure. The solubility of Re in borosilicate glasses was determined to be ~3000 ppm (by mass) using inductively coupled plasma optical emission spectroscopy. At higher rhenium concentrations, additional rhenium was retained in the glasses as crystalline inclusions of alkali perrhenates detected with X-ray diffraction. Since (99)Tc concentrations in a glass waste form are predicted to be <10 ppm (by mass), these Re results implied that the solubility should not be a limiting factor in processing radioactive wastes, assuming Tc as Tc(7+) and similarities between Re(7+) and Tc(7+) behavior in this glass system. PMID:23101883

  12. Characterization of rhenium oxide films and their application to liquid crystal cells

    SciTech Connect

    Cazzanelli, E.; Castriota, M.; Marino, S.; Scaramuzza, N.; Purans, J.; Kuzmin, A.; Kalendarev, R.; Mariotto, G.; Das, G.

    2009-06-01

    Rhenium trioxide exhibits high electronic conductivity, while its open cubic crystal structure allows an appreciable hydrogen intercalation, generating disordered solid phases, with protonic conductivity. Rhenium oxide thin films have been obtained by thermal evaporation of ReO{sub 3} powders on different substrates, maintained at different temperatures, and also by reactive magnetron sputtering of a Re metallic target. A comparative investigation has been carried out on these films, by using micro-Raman spectroscopy and x-ray diffraction. Two basic types of solid phases appear to grow in the films: a red metallic H{sub x}ReO{sub 3} compound, with distorted perovskite structures, like in the bulk material, and ordered HReO{sub 4} crystals based on tetrahedral perrhenate ions. Because of its conduction properties, the electrical and electro-optical behaviors of ReO{sub 3} films deposited on standard indium tin oxide/glass substrate have been tested inside asymmetric nematic liquid crystal cells, showing an appreciable capability of rectification of their electro-optical response, in similar way to tungsten trioxide.

  13. MARE-l in Milan: Status and Perspectives

    NASA Technical Reports Server (NTRS)

    Ferri, E.; Arnaboldi, C.; Ceruti, G.; Faverzani, M.; Gatti, C.; Giachero, A.; Gotti, C.; Kilbourne, C.; Kraft-Bermuth, S.; Nucciotti, A.; Pessini, G.; Schaeffer, D.; Sisti, M.

    2012-01-01

    The international project MARE (Microcalorimeter Array for a Rhenium Experiment) aims at the direct and calorimetric measurement of the electron neutrino mass with sub-eV sensitivity. Although the baseline of the MARE project consists in a large array of rhenium based thermal detectors, a different option for the isotope is also being considered. The different option is Ho-163. The potential of using Re-187 for a calorimetric neutrino mass experiment has been already demonstrated. On the contrary, no calorimetric spectrum of Ho-163 has been so far measured with the precision required to set a useful limit on the neutrino mass. The first phase of the project (MARE-1) is a collection of activities with the aim of sorting out both the best isotope and the most suited detector technology to be used for the final experiment. One of the MARE-1 activities is carried out in Milan by the group of Milano-Bicocca in collaboration with NASA/GSFC and Wisconsin groups. The Milan MARE-l arrays are based on semiconductor thermistors, provided by the NASA/GSFC group, with dielectric silver perrhenate absorbers, AgReO4. The experiment, which is presently being assembled, is designed to host up to 8 arrays.

  14. Separation of technetium from nuclear waste stream simulants. Final report

    SciTech Connect

    Strauss, S.H.

    1995-09-11

    The author studied liquid anion exchangers, such as Aliquat-336 nitrate, various pyridinium nitrates, and related salts, so that they may be applied toward a specific process for extracting (partitioning) and recovering {sup 99}TcO{sub 4}{sup {minus}} from nuclear waste streams. Many of the waste streams are caustic and contain a variety of other ions. For this reason, the author studied waste stream simulants that are caustic and contain appropriate concentrations of selected, relevant ions. Methods of measuring the performance of the exchangers and extractant systems included contact experiments. Batch contact experiments were used to determine the forward and reverse extraction parameters as a function of temperature, contact time, phase ratio, concentration, solvent (diluent), and other physical properties. They were also used for stability and competition studies. Specifically, the author investigated the solvent extraction behavior of salts of perrhenate (ReO{sub 4}{sup {minus}}), a stable (non-radioactive) chemical surrogate for {sup 99}TcO{sub 4}{sup {minus}}. Results are discussed for alternate organic solvents; metalloporphyrins, ferrocenes, and N-cetyl pyridium nitrate as alternate extractant salts; electroactive polymers; and recovery of ReO{sub 4}{sup {minus}} and TcO{sub 4}{sup {minus}}.

  15. SIMS analysis: Development and evaluation 1995 summary report

    SciTech Connect

    Groenewold, G.S.; Appelhans, A.D.; Ingram, J.C.; Delmore, J.E.; Dahl, D.A.

    1995-10-01

    Secondary ion mass spectrometry (SIMS) was evaluated for characterizing Hg salts. It was found that sulfate and chloride species could be identified directly without sample preparation. Mercuric oxide could be identified by complexation with formic acid. Hg nitrates could be identified by complexation with cyclohexylamine (CHA). Laser desorption ion trap MS was evaluated for characterizing EDTA on environmental samples. No intact EDTA ions were observed, but a series of EDTA fragment ions were visible, particularly on basalt and soil. An ion trap SIMS was developed: a perrhenate ion gun was interfaced to a Teledyne ion trap spectrometer, and the entire device was mounted on a cart. The technology was demonstrated using a prototype ion trap SIMS instrument for detecting Hg{center_dot}CHA complexes formed from nitrate salts. Intensity of the ion gun was improved, and the surface damage of the particle was small, and ion gun technology transfer to Phi-Evans, Inc. is being considered. Two technology end users are at INEL`s Central Facilities Area 674 pond and acid pit of the Radioactive Waste Management Complex; target problem at both sites is the need for Hg speciation on soil samples.

  16. Rhenium Radioisotopes for Therapeutic Radiopharmaceutical Development

    SciTech Connect

    Beets, A.L.; Knapp, F.F., Jr.; Kropp, J.; Lin, W.-Y.; Pinkert, J.; Wang, S.-Y.

    1999-01-18

    The availability of therapeutic radioisotopes at reasonable costs is important for applications in nuclear medicine, oncology and interventional cardiology, Rhenium-186 (Re-186) and rhenium-1 88 (Re-188) are two reactor-produced radioisotope which are attractive for a variety of therapeutic applications, Rhenium-186 has a half-life of 90 hours and decays with emission of a &particle with a maximum energy of 1.08 MeV and a 135 keV (9Yo) gamma which permits imaging. In contrast, Re- 188 has a much shorter half-life of 16.9 hours and emits a p-particle with a much higher energy of 2.12 MeV (Em=) and a 155 keV gamma photon (15Yo) for imaging. While Re-186 is unavailable from a generator system and must be directly produced in a nuclear reactor, Re-188 can also be directly produced in a reactor with high specific activity, but is more conveniently and cost-effectively available as carrier-free sodium perrhenate by saline elution of the alumina-based tungsten-188 (W1 88)/Re-l 88 generator system [1-2]. Since a comprehensive overviewofRe-186 and Re-188 therapeutic agents is beyond the scope of this &tended Abstrac4 the goal is to provide key examples of various agents currently in clinical use and those which are being developed for important clinical applications.

  17. Use of a new tandem cation/anion exchange system with clinical-scale generators provides high specific volume solutions of technetium-99m and rhenium-188

    SciTech Connect

    Knapp, F.R. Jr.; Beets, A.L.; Mirzadeh, S.; Guhlke, S. |

    1998-03-01

    In this paper the authors describe the first application of a simple and inexpensive post elution tandem cation-anion exchange column system which is based on generator elution with salts of weak acids such as ammonium acetate instead of saline solution to provide very high specific volume solutions of technetium-99m and rhenium-188 from clinical scale molybdenum-99/technetium-99m generator prepared from low specific activity (n,y) molybdenum-99, and tungsten-188/rhenium-188 generators, respectively. Initial passage of the bolus through a strong cation exchange cartridge converts the ammonium acetate to acetic acid which is essentially not ionized at the acidic pH, allowing specific subsequent amine type (QMA SepPak{trademark}) anion exchange cartridge column trapping of the microscopic levels of the pertechnetate or perrhenate. Subsequent elution of the anion cartridge with a small volume (< 1 mL) of saline then provides high specific volume solutions of technetium-99m by concentration of the high eluant volumes obtained by elution of clinical-scale (1 Ci) generators. This new approach also works very effectively to obtain high specific volume solutions of rhenium-188 (> 500 mCi/mL) from the alumina-based tungsten-188/rhenium-188 generator.

  18. Crystallization of rhenium salts in a simulated low-activity waste borosilicate glass

    SciTech Connect

    Riley, Brian J.; McCloy, John S.; Goel, Ashutosh; Liezers, Martin; Schweiger, Michael J.; Liu, Juan; Rodriguez, Carmen P.; Kim, Dong-Sang

    2013-04-01

    This study presents a new method for looking at the solubility of volatile species in simulated low-activity waste glass. The present study looking at rhenium salts is also applicable to real applications involving radioactive technetium salts. In this synthesis method, oxide glass powder is mixed with the volatiles species, vacuum-sealed in a fused quartz ampoule, and then heat-treated under vacuum in a furnace. This technique restricts the volatile species to the headspace above the melt but still within the sealed ampoule, thus maximizing the volatile concentration in contact with the glass. Various techniques were used to measure the solubility of rhenium in glass and include energy dispersive spectroscopy, wavelength dispersive spectroscopy, laser ablation inductively-coupled plasma mass spectroscopy, and inductively-coupled plasma optical emission spectroscopy. The Re-solubility in this glass was determined to be ~3004 parts per million Re atoms. Above this concentration, the salts separated out of the melt as inclusions and as a low viscosity molten salt phase on top of the melt observed during and after cooling. This salt phase was analyzed with X-ray diffraction, scanning electron microscopy as well as some of the other aforementioned techniques and identified to be composed of alkali perrhenate and alkali sulfate.

  19. Plant root absorption and metabolic fate of technetium in plants

    SciTech Connect

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

    1984-10-01

    Root absorption characteristics for the pertechnetate ion (TcO/sub 4//sup -/) were determined using hydroponically grown soybean seedlings (Glycine max, cv. Williams). Absorption of TcO/sub 4//sup -/ was found to be linear with time, sensitive to metabolic inhibitors, and exhibit multiple absorption isotherms over the concentration range 0.02 to 10 ..mu..M. The isotherms had calculated K/sub s/ values of 0.09, 8.9, and 54 ..mu..M for intact seedlings. The uptake of TcO/sub 4//sup -/ (0.25 ..mu..M) was inhibited by a fourfold concentration excess of sulfate, phosphate, and selenate, but not by borate, nitrate, tungstate, perrhenate, iodate or vanadate. Kinetic studies demonstrated that sulfate, phosphate, and selenate were competitive inhibitors of TcO/sub 4//sup -/ absorption. Once absorbed, Tc was readily transported as TcO/sub 4//sup -/ to shoot tissues of soybean and subsequently associated with protein constituents. The chemical fate of Tc in plants varies with plant species. Plants high in nonprotein sulfhydryl compounds (Allium species) exhibited markedly different root/shoot distribution and protein incorporation patterns from species with low sulfur requirements (soybean, alfalfa, mustard). Based on these differences, Tc/S/Se tracer studies were employed to resolve the comparative fate of these probable analogs. 20 references, 5 figures, 5 tables.

  20. Structural and magnetic properties of quasi-1 and 2D pyrazine-containing spin-1/2 antiferromagnets.

    SciTech Connect

    Manson, J. L.; Connor, M. M.; Schlueter, J. A.; Hyzer, K. A.; Kykeem, A.; Materials Science Division; Eastern Washington Univ.

    2007-06-01

    Aqueous reaction of Cu(BF{sub 4}){sub 2}, NH{sub 4}HF{sub 2}, and pyrazine leads to formation of a novel 3D framework, [Cu(HF{sub 2})(pyz){sub 2}]BF{sub 4} (1), where 2D [Cu(pyz){sub 2}]{sup 2+} square layers are connected via HF{sub 2}{sup -}. A second compound, Cu(ReO{sub 4}){sub 2}(H{sub 2}O){sub 2}(pyz) (2), was the result of our attempt to create the perrhenate analog of 1; a linear chain compound consisting of CuO{sub 4}N{sub 2} octahedra linked through pyrazine ligands formed instead. Both compounds exhibit extensive hydrogen bonding interactions where bifluoride, F...H...F{sup -}, and O-H...O link layers and chains together in 1 and 2, respectively. Broad maxima indicative of short-range magnetic ordering (SRO) were observed in the magnetic susceptibility at 5.5 (1) and 7.7 K (2) while no evidence for the transition to long-range magnetic ordering (LRO) was detected above 2 K.

  1. Radiant{trademark} Liquid Radioisotope Intravascular Radiation Therapy System

    SciTech Connect

    Eigler, N.; Whiting, J.; Chernomorsky, A.; Jackson, J.; Knapp, F.F., Jr.; Litvack, F.

    1998-01-16

    RADIANT{trademark} is manufactured by United States Surgical Corporation, Vascular Therapies Division, (formerly Progressive Angioplasty Systems). The system comprises a liquid {beta}-radiation source, a shielded isolation/transfer device (ISAT), modified over-the-wire or rapid exchange delivery balloons, and accessory kits. The liquid {beta}-source is Rhenium-188 in the form of sodium perrhenate (NaReO{sub 4}), Rhenium-188 is primarily a {beta}-emitter with a physical half-life of 17.0 hours. The maximum energy of the {beta}-particles is 2.1 MeV. The source is produced daily in the nuclear pharmacy hot lab by eluting a Tungsten-188/Rhenium-188 generator manufactured by Oak Ridge National Laboratory (ORNL). Using anion exchange columns and Millipore filters the effluent is concentrated to approximately 100 mCi/ml, calibrated, and loaded into the (ISAT) which is subsequently transported to the cardiac catheterization laboratory. The delivery catheters are modified Champion{trademark} over-the-wire, and TNT{trademark} rapid exchange stent delivery balloons. These balloons have thickened polyethylene walls to augment puncture resistance; dual radio-opaque markers and specially configured connectors.

  2. Design and construction of a imaging instrument for studying ion emission from pure ion emitters

    SciTech Connect

    Olson, J.E.

    1993-09-01

    The development of new ion sources is important in the area of surface analysis to make it easier to perform more sensitive and accurate analyses. In surface analysis a primary ion beam composed of a single species can help when predicting and interpreting the results. Therefore, much interest and effort has been focused on producing pure ion emitters. An instrument has been designed and constructed to view the current densities of the ions being emitted from pure ion emitters. The instrument electrostatically accelerates and focuses the ion beam onto a microchannel plate detector equipped with a phosphor screen for viewing the images. These images are used to identify areas of enhanced ion emission. Once these areas are identified, the investigator can use other instruments to analyze them, and hopefully develop a better understanding of the chemistry and physics involved in the ion emission process. A computer based control system has been integrated into the system to simplify the operation of the instrument and provide safety features to protect the hardware from damage. A closed-circuit video camera system is used to allow the images to be remotely viewed during imaging procedures. Experiments show that the instrument has a lower detection limit of 7.45 {times} 10{sup 3} ions/sec/mm{sup 2} and a spatial resolution of approximately 3 {minus} 4 {mu}m. Results from imaging cesium zeolite and perrhenate ion sources indicate that the ions are primarily being emitted from the surface of the sources and not from the interfacial region between the substrate and the emitter material.

  3. A Freeze-Dried Kit for the Preparation of (188)Re-HEDP for Bone Pain Palliation: Preparation and Preliminary Clinical Evaluation.

    PubMed

    Mallia, Madhava B; Shinto, Ajit Sugunan; Kameswaran, Mythili; Kamaleshwaran, Koramadai Karuppusamy; Kalarikal, Radhakrishnan; Aswathy, K K; Banerjee, Sharmila

    2016-05-01

    (188)Re-HEDP is an established radiopharmaceutical used for pain palliation in patients with osseous metastasis. Considering commercial availability of (188)W/(188)Re generator, the accessibility to a lyophilized kit would make preparation of this radiopharmaceutical feasible at the hospital radiopharmacy having access to a generator. A protocol for the preparation of a single-vial lyophilized hydroxyethane 1,1-diphosphonic acid (HEDP) kit was developed and its consistency was checked by preparing six batches. Each sterile lyophilized kit prepared as per the protocol contained 9 mg of HEDP, 3 mg of gentisic acid, and 4 mg of SnCl2.2H2O. Randomly selected kits from all six batches were subjected to thorough quality control tests that were passed by all batches. (188)Re-HEDP could be prepared by addition of 1 mL of freshly eluted Na(188)ReO4 (up to 3700 MBq) containing 1 μmol of carrier ReO4(-) (perrhenate) and heating at 100°C for 15 minutes. (188)Re-HEDP with >95% radiochemical purity could be consistently prepared using the lyophilized kits. Sterile (188)Re-HEDP prepared using the lyophilized kit was evaluated in patients with osseous metastasis. Post-therapy images of the patient were compared with (99m)Tc-MDP bone scan and found to be satisfactory. The bone-to-background as well as tumor-to-normal bone uptake ratio was found to be significant. All patients who received therapy reported significant pain relief within a week to 10 days post-administration of (188)Re-HEDP. PMID:27183437

  4. DOE FG02-03ER63557: Final Technical Report: Reactivity of Primary Soil Minerals and Secondary Precipitates Beneath Leaking Hanford Waste Tanks

    SciTech Connect

    Kathryn L. Nagy

    2009-05-04

    The purpose of the project was to investigate rates and mechanisms of reactions between primary sediment minerals and key components of waste tank solutions that leaked into the subsurface at the Hanford Site. Results were expected to enhance understanding of processes that cause (1) changes in porosity and permeability of the sediment and resultant changes in flow paths of the contaminant plumes, (2) formation of secondary precipitates that can take up contaminants in their structures, and (3) release of mineral components that can drive redox reactions affecting dissolved contaminant mobility. Measured rates can also be used directly in reactive transport models. Project tasks included (1) measurement of the dissolution rates of biotite mica from low to high pH and over a range of temperature relevant to the Hanford subsurface, (2) measurement of dissolution rates of quartz at high pH and in the presence of dissolved alumina, (3) measurement of the dissolution rates of plagioclase feldspar in high pH, high nitrate, high Al-bearing solutions characteristic of the BX tank farms, (4) incorporation of perrhenate in iron-oxide minerals as a function of pH, and (5) initiation of experiments to measure the formation of uranium(VI)-silicate phases under ambient conditions. Task 2 was started under a previous grant from the Environmental Management Science Program and Task 4 was partially supported by a grant to the PI from the Geosciences Program, Office of Basic Energy Sciences. Task 5 was continued under a subsequent grant from the Environmental Remediation Sciences Program, Office of Biological and Environmental Research.

  5. RHENIUM SOLUBILITY IN BOROSILICATE NUCLEAR WASTE GLASS IMPLICATIONS FOR THE PROCESSING AND IMMOBILIZATION OF TECHNETIUM-99 (AND SUPPORTING INFORMATION WITH GRAPHICAL ABSTRACT)

    SciTech Connect

    AA KRUGER; A GOEL; CP RODRIGUEZ; JS MCCLOY; MJ SCHWEIGER; WW LUKENS; JR, BJ RILEY; D KIM; M LIEZERS; P HRMA

    2012-08-13

    The immobilization of 99Tc in a suitable host matrix has proved a challenging task for researchers in the nuclear waste community around the world. At the Hanford site in Washington State in the U.S., the total amount of 99Tc in low-activity waste (LAW) is {approx} 1,300 kg and the current strategy is to immobilize the 99Tc in borosilicate glass with vitrification. In this context, the present article reports on the solubility and retention of rhenium, a nonradioactive surrogate for 99Tc, in a LAW sodium borosilicate glass. Due to the radioactive nature of technetium, rhenium was chosen as a simulant because of previously established similarities in ionic radii and other chemical aspects. The glasses containing target Re concentrations varying from 0 to10,000 ppm by mass were synthesized in vacuum-sealed quartz ampoules to minimize the loss of Re by volatilization during melting at 1000 DC. The rhenium was found to be present predominantly as Re7 + in all the glasses as observed by X-ray absorption near-edge structure (XANES). The solubility of Re in borosilicate glasses was determined to be {approx}3,000 ppm (by mass) using inductively coupled plasma-optical emission spectroscopy (ICP-OES). At higher rhenium concentrations, some additional material was retained in the glasses in the form of alkali perrhenate crystalline inclusions detected by X-ray diffraction (XRD) and laser ablation-ICP mass spectrometry (LA-ICP-MS). Assuming justifiably substantial similarities between Re7 + and Tc 7+ behavior in this glass system, these results implied that the processing and immobilization of 99Tc from radioactive wastes should not be limited by the solubility of 99Tc in borosilicate LAW glasses.

  6. Palliation and Survival After Repeated Re-188-HEDP Therapy of Hormone-Refractory Bone Metastases of Prostate Cancer: A Retrospsective Analysis

    SciTech Connect

    Knapp Jr, Russ F

    2011-01-01

    This retrospective study compared the effects of single and multiple administrations of {sup 186}Re-hydroxyethylidenediphosphonate (186Re-HEDP) on palliation and survival of prostate cancer patients presenting with more than 5 skeletal metastases. Methods: A total of 60 patients were divided into 3 groups. Group A (n = 19) consisted of patients who had received a single injection; group B (n = 19), patients who had 2 injections; and group C (n = 22), patients who had 3 or more successive injections. The {sup 188}Re-HEDP was prepared using non-carrier-added {sup 188}Re obtained from an in-house {sup 188}W/{sup 188}Re generator after dilution with carrier perrhenate. Patients data available from the referring physicians - including prostate-specific antigen levels - were entered into a Windows-based matrix and analyzed using a statistical program. The Gleason scores were similar for all 3 groups. Results: Mean survival from the start of treatment was 4.50 {+-} 0.81 mo (95% confidence interval [CI], 2.92-6.08) for group A, 9.98 {+-} 2.21 mo (95% CI, 5.65-14.31) for group B, and 15.66 {+-} 3.23 (95% CI, 9.33-22.0) for group C. Although the 3 groups did not differ in Gleason score, the number of lost life-years was significantly lower in group C than in groups A and B. Pain palliation was achieved in 89.5% of group A, 94.7% of group B, and 90.9% of group C. Conclusion: Posttreatment overall survival could be improved from 4.50 to 15.66 mo by multiple-injection bone-targeted therapy with {sup 188}Re-HEDP, when compared with a single injection. Significant pain palliation was common and independent of administration frequency.

  7. Ultra-small rhenium nanoparticles immobilized on DNA scaffolds: An excellent material for surface enhanced Raman scattering and catalysis studies.

    PubMed

    Anantharaj, S; Sakthikumar, K; Elangovan, Ayyapan; Ravi, G; Karthik, T; Kundu, Subrata

    2016-12-01

    Highly Sensitive and ultra-small Rhenium (Re) metal nanoparticles (NPs) were successfully stabilized in water by the staging and fencing action of the versatile biomolecule DNA that resulted in two distinct aggregated chain-like morphologies with average grain sizes of 1.1±0.1nm and 0.7±0.1nm for the very first time within a minute of reaction time. Re NPs are formed by the borohydride reduction of ammonium perrhenate (NH4ReO4) in the presence of DNA at room temperature (RT) under stirring. The morphologies were controlled by carefully monitoring the molar ratio of NH4ReO4 and DNA. The synthesized material was employed in two potential applications: as a substrate for surface enhanced Raman scattering (SERS) studies and as a catalyst for the reduction of aromatic nitro compounds. SERS study was carried out by taking methylene blue (MB) as the probe and the highest SERS enhancement factor (EF) of 2.07×10(7) was found for the aggregated chain-like having average grain size of 0.7±0.1nm. Catalytic reduction of 4-nitro phenol (4-NP), 2-nitro phenol (2-NP) and 4-nitroaniline (4-NA) with a rate constant value of 6×10(-2)min(-1), 33.83×10(-2)min(-1) and 37.4×10(-2)min(-1) have testified the excellent catalytic performance of our Re NPs immobilized on DNA. The overall study have revealed the capability of DNA in stabilizing the highly reactive Re metal at nanoscale and made them applicable in practice. The present route can also be extended to prepare one dimensional (1-D), self-assembled NPs of other reactive metals, mixed metals or even metal oxides for specific applications in water based solutions. PMID:27571687

  8. Preparation and initial characterization of fluidized bed steam reforming pure-phase standards

    SciTech Connect

    Missimer, D. M.; Rutherford, R. L.

    2013-03-21

    Hanford is investigating the Fluidized Bed Steam Reforming (FBSR) process for their Low Activity Waste. The FBSR process offers a low-temperature continuous method by which liquid waste can be processed with the addition of clay into a sodium aluminosilicate (NAS) waste form. The NAS waste form is mainly comprised of nepheline (NaAlSiO{sub 4}), sodalite (Na{sub 8}[AlSiO{sub 4}]{sub 6}Cl{sub 2}), and nosean (Na{sub 8}[AlSiO{sub 4}]{sub 6}SO{sub 4}). Anions such as perrhenate (ReO{sub 4}{sup -}), pertechnetate (TcO{sub 4}{sup -}), and iodine (I{sup -}) are expected to replace sulfate in the nosean structure and/or chloride in the sodalite mineral structure (atomically bonded inside the aluminosilicate cages that these mineral structures possess). In the FBSR waste form, each of these phases can exist in a variety of solid solutions that differ from the idealized forms observed in single crystals in nature. The lack of understanding of the durability of these stoichiometric or idealized mineral phases complicates the ability to deconvolute the durability of the mixed phase FBSR product since it is a combination of different NAS phases. To better understand the behavior, fabrication and testing of the individual phases of the FBSR product is required. Analytical Development (AD) of the Science and Technology directorate of the Savannah River National Laboratory (SRNL) was requested to prepare the series of phase-pure standards, consisting of nepheline, nosean, and Cl, Re, and I sodalite. Once prepared, X-ray Diffraction (XRD) analyses were used to confirm the products were phase pure. These standards are being used for subsequent characterization studies consisting of the following: single-pass flow-through (SPFT) testing, development of thermodynamic data, and x-ray diffraction (XRD) calibration curves. In addition to the above mentioned phase-pure standards, AD was tasked with fabricating a mixed Tc-Re sodalite.

  9. Mechanism and Mitigation of the Decomposition of an Oxorhenium Complex-Based Heterogeneous Catalyst for Perchlorate Reduction in Water.

    PubMed

    Liu, Jinyong; Chen, Xi; Wang, Yin; Strathmann, Timothy J; Werth, Charles J

    2015-11-01

    A biomimetic heterogeneous catalyst combining palladium nanoparticles and an organic ligand-coordinated oxorhenium complex on activated carbon, Re(hoz)2-Pd/C, was previously developed and shown to reduce aqueous perchlorate (ClO4-) with H2 at a rate ∼100 times faster than the first generation ReOx-Pd/C catalyst prepared from perrhenate (ReO4-). However, the immobilized Re(hoz)2 complex was shown to partially decompose and leach into water as ReO4-, leading to an irreversible loss of catalytic activity. In this work, the stability of the immobilized Re(hoz)2 complex is shown to depend on kinetic competition between three processes: (1) ReV(hoz)2 oxidation by ClO4- and its reduction intermediates ClOx-, (2) ReVII(hoz)2 reduction by Pd-activated hydrogen, and (3) hydrolytic ReVII(hoz)2 decomposition. When ReV(hoz)2 oxidation is faster than ReVII(hoz)2 reduction, the ReVII(hoz)2 concentration builds up and leads to hydrolytic decomposition to ReO4- and free hoz ligand. Rapid ReV(hoz)2 oxidation is mainly promoted by highly reactive ClOx- formed from the reduction of ClO4-. To mitigate Re(hoz)2 decomposition and preserve catalytic activity, ruthenium (Ru) and rhodium (Rh) were evaluated as alternative H2 activators to Pd. Rh showed superior activity for reducing the ClO3- intermediate to Cl-, thereby preventing ClOx- buildup and lowering Re complex decomposition in the Re(hoz)2-Rh/C catalyst. In contrast, Ru showed the lowest ClO3- reduction activity and resulted in the most Re(hoz)2 decomposition among the Re(hoz)2-M/C catalysts. This work highlights the importance of using mechanistic insights from kinetic and spectroscopic tests to rationally design water treatment catalysts for enhanced performance and stability. PMID:26422179

  10. Tc and Re behavior in borosilicate waste glass vapor hydration tests.

    PubMed

    McKeown, David A; Buechele, Andrew C; Lukens, Wayne W; Shuh, David K; Pegg, Ian L

    2007-01-15

    Technetium, found in some nuclear wastes (such as those generated from spent fuel reprocessing), is of particular concern with regard to long-term waste storage because of its long half-life (2.13 x 10(5) years) and high mobility in the environment. One method of stabilization of such waste is through vitrification to produce a durable borosilicate glass matrix. The fate of Tc under hydrothermal conditions in the vapor hydration test (VHT) was studied to assess and possibly predict the long-term rate of release of Tc from borosilicate waste glass. For comparison, the fate of rhenium, the preferred nonradioactive surrogate for Tc, was similarly studied. X-ray absorption spectroscopy (XAS) and scanning electron microscopy (SEM) measurements were made on each original borosilicate glass and the corresponding sample after the VHT. Tc K-edge XAS indicates that, despite starting with different Tc(IV) and Tc(VII) distributions in each glass, both corresponding VHT samples contain 100% Tc(IV). The Tc reduction within the VHT samples may be driven by the low-oxygen atmosphere compounded by oxygen depletion from corrosion of the surrounding stainless steel vessel. From SEM analyses, both of the Tc-containing VHT samples show complete alteration of the original glass, significant Tc enrichment near the sample surface, and nearly complete depletion of Tc toward the sample center. XAS indicates Tc(IV)O6 octahedra, possibly within gel-like amorphous silicates in both VHT samples, where Tc-Tc correlations are observed in the higher Tc-content VHT sample. Re L(II)-edge XAS and SEM indicate quite different behavior for Re under VHT conditions. The Re oxidation state appears to be invariant with respect to the VHT treatment, where perrhenate (Re(VII)) species are dominant in all Re-containing samples investigated; Re2O7 concentrations are low near the sample surface and increase to approach that of the unreacted glass toward the sample center. PMID:17310703

  11. Expression profile of vascular cell adhesion molecule-1 (CD106) in inflammatory foci using rhenium-188 labelled monoclonal antibody in mice.

    PubMed

    Kairemo, K J; Strömberg, S; Nikula, T K; Karonen, S L

    1998-06-01

    Rhenium (Re)-188 is a generator (W-188/Re-188) produced high energy beta-emitter suitable for radionuclide therapy (T1/2 is 16.9 hrs and Emax 2.1 MeV (range 11 mm)). We have labelled monoclonal antibody (MAb) raised against vascular cell adhesion molecule-1 (VCAM-1) with Re-188 using glucoheptonate chelation technique and SnCl2 as reducing agent. The labelling efficiency, free perrhenate and reduced Re were controlled with thin layer chromatography and the purification of Re-188-MoAbs was performed using gel filtration. Our results indicate that Re-188-labelled antibodies remain in vitro stable and the labelling purity is > 90%. We also have applied these Re-188-MoAbs for detection of inflammatory disease in a mouse. The effective half-lives of organs of interest after an injection of Re-188-anti-VCAM1 were as follows: blood 5.2 hr, kidney 4.7 hr, and liver 9.6 hr. Re-188-anti-VCAM-1 was found to accumulate mainly in kidney and liver. One hour after the injection, the kidney contained in average as high as 12.5% and the liver 2.8 ID/g tissue. After 6 hr, the kidney contained 5.5% ID/g and the liver 2.6% ID/g. At 24 hr, the kidney uptake was 0.5% ID/g and the liver uptake 0.8% ID/g, respectively. The inflamed foci, subcutaneous lesions in the footpad skin, were visualized using gamma camera. From the distribution data the uptakes in the inflamed foci as follows: at 1 hr 2.18 (inflammation) and 1.72% ID/g (control), at 6 hr 1.42 (inflammation) and 0.85% ID/g (control), and at 24 hr 0.17 (inflammation) and 0.084% ID/g (control), respectively. Anti-VCAM-1 MAb showed better targeting as compared to control MoAbs in inflammation (caused by E.coli lipoplysaccaride). In conclusion, Re-188 is suitable for MAb labelling, and MAb against VCAM-1 may be used for detection of local inflammatory disease. PMID:9762472

  12. 188Re-ethylene dicysteine: a novel agent for possible use in endovascular radiation therapy.

    PubMed

    Das, T; Banerjee, S; Samuel, G; Sarma, H D; Ramamoorthy, N; Pillai, M R

    2000-10-01

    Several agents, such as 188ReO4-, 188Re-MAG3 and 188Re-DTPA are currently under investigation as radiation sources in liquid-filled balloons for prevention of restenosis following coronary angioplasty. Bearing in mind the risk factor associated with leakage of radioactivity in the event of balloon rupture, the criteria sought in selecting suitable agents for endovascular radiation therapy (EVRT) are rapid clearance and low dose to vital organs. Since 99Tcm labelled ethylene dicysteine (EC) is a well established agent for renal tubular function imaging, the use of 186Re-ethylene dicysteine as a potential agent for prevention of restenosis after angioplasty has been evaluated previously. Therefore, it was of interest to evaluate the applicability of the more potential isotope of rhenium, 188Re, a high energy beta-emitter (Ebetamax = 2.12 MeV) with a suitable T 1/2 = 16.9 h, obtainable carrier-free from the 188W-188Re generator, as an attractive and alternative radionuclide for labelling with L,L-EC. In this paper, the preparation and pharmacological behaviour of the 188Re complex of ethylene dicysteine are reported. The complex can be prepared in high yields (99.5%) under optimized conditions of pH 2-3, at a ligand concentration of 15 mM, 50 microg (0.18 mM) carrier rhenium and using 2 mg x mL(-1) stannous chloride. On storage at 4 degrees C, the RC purity was more than 97% after 48 h when prepared under optimum conditions. Biodistribution studies in Wistar rats showed the desired characteristics of fast blood clearance and low retention of activity in the vital organs (< 2% in intestine, < 1% in stomach, < 0.5% in liver) with a high renal excretion (90.65+/-0.6%) at 3 h post-injection. These results confirm the advantages of using the 188Re-EC complex compared with perrhenate and other rhenium radiopharmaceuticals currently being used in balloons for EVRT. PMID:11130335

  13. Technetium (VII) Co-precipitation with Framework Aluminosilicates

    SciTech Connect

    Harsh, James B.; Dickson, Johnbull Otah; Pierce, Eric M.; Bargar, John

    2015-07-13

    Technetium-99 (99Tc), a long-lived radionuclide, is one of the most widespread contaminants within the Hanford subsurface. At some depths, it is only extractable with strong acids, suggesting incorporation into a solid phase. We hypothesized that Tc may have coprecipitated with feldspathoid aluminosilicates under waste tanks that had leaked caustic solutions into the vadose zone. Our objectives were to determine if Tc could be incorporated into the feldspathoids cancrinite and sodalite and under what conditions coprecipitation could occur. Our hypothesis was that sodalite was more likely to incorporate and retain Tc. Our approach was to use known methods of feldspathoid formation in solutions resembling those in Hanford waste tanks contacting sediments in terms of major ion (Na, NO3, OH, Al(OH)4, and Si(OH)4 concentrations. In some cases, Al and Si were supplied from zeolite. We used perrhenate (ReO4) as a surrogate for pertechnetate (TcO4) to avoid the radioactivity. The major findings of this study were 1) ReO4 could be incorporated into either sodalite or cancrinite but the concentration in the solid was < 1% of the competing ion Cl, NO3, or NO2. 2) The small amount of ReO4 incorporated was not exchangeable with NO3 or NO2. 3) In sodalite, NO3 was highly preferred over ReO4 but significant Re-sodalite was formed when the mole fraction in solution (Re/Re+N) exceeded 0.8. 4) A nonlinear relation between the unit cell parameter and amount of Re incorporated suggested that a separate Re-sodalite phase was formed rather than a solid solution. 5) We determined that sodalite preference for sodalite in the presence of different anions increased with the ionic size of the competing anion: Cl < CO3 < NO3 < SO4 < MnO4 < WO4 and significant incorporation did not occur unless the difference in anion radii was less than 12%. 6) Re(VII) was not significantly reduced to Re(IV) under the conditions of this experiment and Re appeared to be a good surrogate for Tc under oxidizing

  14. Investigation and development of liquid-liquid extraction systems for the removal of pertechnetate from aqueous nuclear waste stream simulants

    NASA Astrophysics Data System (ADS)

    Gansle, Kristina Marie Rohal

    1998-11-01

    The solvent extraction behavior of perrhenate (ReO 4-) and pertechnetate (TcO4- ) from aqueous nuclear waste stream simulants was examined using the anion-exchange reagent Aliquat-336 nitrate. The extraction tendencies of ReO 4- followed those of TcO4- from both acidic and basic media, demonstrating that ReO4 - was a suitable nonradioactive surrogate for TcO4 -. For ICP-AES analysis of Re in high salt solutions, a V-groove nebulizer and 1:1 dilution of the sample and standards with 0.1% Triton X-100 surfactant reduced deposition of solids within the sample introduction system, thus minimizing memory effects. A new approach to waste remediation technology, Redox-Recyclable Extraction and Recovery (R2ER), was also studied. The redox-active species 1,1',3,3'-tetrakis(2-methyl-2-hexyl)ferrocene (HEP) was oxidized to its cationic form for extraction of TcO4 - or ReO4- from aqueous waste and reduced to its neutral form for recovery of the anion. The thermodynamics of liquid-liquid interfacial electron transfer for the oxidation/activation of HEP were shown to be controlled by three factors: the reduction potentials of the redox-active species in the aqueous and organic phases and the transfer of an ion across the liquid-liquid interface. The deactivation/reduction rate of HEP+NO3- by iron was affected by organic solvent diluent and improved by treating the iron with hexanes and 1 M HCl. The volume of solid secondary-waste in the R2ER cycle was reduced by a factor of 3000. In complete extraction/recovery cycles, HEP+NO3- in 2-nonanone removed greater than 99% TcO4- from the 101-SY, 103-SY, 1 M HCl and 1 M NaOH/1.5 M NaNO3 Hanford Tank waste simulants. Another redox-active extractant, bis(hydridotris(1-pyrazolyl)borato)iron(III) nitrate (FeTp2+NO3-), was also selective for ReO4- remediation from simulated aqueous waste. Organic solutions of the alkyl substituted ferricenium extractants were not stable in the presence of nucleophilic anions and/or reducing agents. HEP+NO3