Sorption of radionuclides by microorganisms from a deep repository of liquid low-level waste

Sorption of radionuclides on a biomass of aerobic microorganisms isolated from deep repositories of liquid low-level waste was examined. Each strain exhibited substantially different sorption of different radionuclides. In neutral medium, the maximal proportion of the recovered radionuclides was 77, 92, 76, 72, and 33% for Pu, Np, U, Am, and Sr, respectively. None of the isolated strains sorbed Cs. The highest sorption ability was exhibited by Pseudomonas genus bacteria. The results obtained are indicative of different mechanisms of interactions of microorganisms with radionuclides.     

Separation of U,Pu, and Am recovered from mixed oxide (MOX) fuel by countercurrent chromatography

The separation of U, Pu, and Am recovered from MOX fuel with the adduct of HNO₃ with N,N′-dimethyl-N,N′-dioctylhexylethoxymalonamide by countercurrent chromatography (CCC) was studied. Solutions of N,N′-dimethyl-N,N′-dibutyldodecylethoxymalonamide in dodecane were used as stationary phase. The separation of U, Pu, and Am was carried in both isocratic and stepwise elution modes. The better separation of actinides and their higher radionuclidic purity are reached with stepwise elution. The first eluate fraction contained only Am (100%). The second eluate fraction contained U (100%) and Pu (0.7%). The third eluate fraction contained 99.3% of Pu.     

Disproportionation of Pu(V) in K<Subscript>10</Subscript>P<Subscript>2</Subscript>W<Subscript>17</Subscript>O<Subscript>61</Subscript> solutions

In solutions of unsaturated heteropolytungstate K₁₀P₂W₁₇O₆₁, Pu(V) disproportionates in a wide pH range; it is a first-order reaction with respect to Pu(V), and its rate only slightly changes in the pH range from 0.7 to 4.0. The activation energy E _a of Pu(V) disproportionation was determined as 78.6±2.0 and 64.2±3 kJ mol^?1 at pH 2.0±0.1 and 4.0±0.2, respectively. The thermodynamic parameters of activation ΔH ^≠ and ΔS ^≠ were evaluated. Published data on disproportionation of Np(V) and Am(V) in K₁₀P₂W₁₇O₆₁ solutions were analyzed.     

Synthesis and Structure of Mixed Cromate–Nitrate Complexes of Hexavalent Actinides, [(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>N][(AnO<Subscript>2</Subscript>)(CrO<Subscript>4</Subscript>)(NO<Subscript>3</Subscript>)] (An = U,Np, Pu)

Mixed-anion compounds of the general composition [(CH₃)₄N][(AnO₂)(CrO₄)(NO₃)], where An = U, Np, and Pu, were synthesized and structurally characterized. The structural motif of these compounds is based on anionic ribbons of the composition [AnO₂(NO₃)(CrO₄)]_n^n–, consisting of seven-vertex An polyhedra linked via oppositely oriented CrO₄ tetrahedra and NO₃ groups acting in the An polyhedra as terminal bidentate ligands. Every four anionic ribbons form channels oriented along b-axis. Tetramethylammonium cations linked with the O atoms of the ribbons by hydrogen bonds are located in these channels. Actinide contraction is observed in the series U–Np–Pu. It is manifested in a regular decrease in the interatomic distances in the An polyhedra, in parameters b and c, and in the unit cell volume.     

Sorption-barrier properties of granitoids and andesite-basaltic metavolcanites with respect to Am(III) and Pu(IV): 1. Absorption of Am and Pu from groundwater on monolithic samples of granitoids and andesite-basaltic metavolcanites

A model study is made of the sorption-barrier properties of intact monolithic samples of granitoids and andesite-basaltic metavolcanites with respect to Am(III) and Pu(IV). In sorption from simulated groundwater (pH 8.3), the surface distribution coefficient in surface sorption K _a was determined to be 8–37 and 4–80 cm for Am and Pu, respectively. The mineral components of the rocks responsible for the radionuclide sorption were identified by autoradiography. The rocks tested are characterized by high retention capacity for Am and Pu.     

Synthesis and study of Np(V) and Pu(V) benzoate complexes with bipyridine

Heteroligand compounds AnO₂(bipy)OOCC₆H₅ (An = Np, Pu; bipy = α,α-bipyridine, C¹⁰H⁸N²) were synthesized and studied. It follows from powder X-ray patterns that these compounds are isostructural. Their unit cell parameters, determined by indexing of the powder X-ray patterns, are as follows: a = 9.2162 (7), b = 10.2339(8), c = 17.4083(17) Å, and β = 96.48(1)° for Np and a = 9.1983(18), b = 10.2052(18), c = 17.370(3) Å and β = 96.51(1)° for Pu. The compounds crystallize in the monoclinic system space group P2₁/n, Z = 4. The electronic absorption spectra of crystalline compounds suggest pentagonal-bipyramidal surrounding of the central atom and the prescence of cation-cation bonds with AnO ₂ ⁺ ions acting as monodentate ligands with respect to each other. The IR spectra of the compounds were recorded, and their thermal behavior in air was studied.     

Extraction of long-lived radionuclides from nitric acid solutions using an extractant based on dibutyl hydrogen phosphate and chlorinated cobalt dicarbollide

Chlorinated cobalt dicarbollide (CCD), when added to concentrations of 0.25 M to a solution of dibutyl hydrogen phosphate (HDBP) in m-nitrobenzotrifluoride (MNBTF), increases the distribution ratios of trace amounts of Eu and Am without changing the slope (tan α ～ 2) of their dependences on HDBP concentration in the 0–1.5 M range. At [CCD]/([CCD] + DBPA]) = 0.2–0.22, the synergistic effect is observed in the entire range of HDBP concentrations in extraction of these elements from 1.0 and 2.5 M HNO₃. In this case, HDBP suppresses the extraction of Cs with CCD in the area below the synergistic maximum, where antagonism is observed in the extraction of Cs. Polyethylene glycol (PEG, Slovafol-909) was added to the extraction mixture to improve the extraction of Sr. The extremum is attained at its concentration in the solvent with HDBP of ～0.033–0.065 M, which is smaller than that in the absence of HDBP by a factor of 1.5–2.5. With increasing concentration of HDBP in the HDBP-CCD-PEG-MNBTF extraction system, the slopes for Eu and Am are 1.3 and 0.6, whereas the slopes for Cs and Sr decrease nonlinearly and amount to ?1.8 and ?1.3, respectively. With increasing concentration of HNO₃, D for Eu, Am, and Cm decreases in proportion to the HNO₃ concentration to the power of ?3 irrespective of the PEG concentration, and for Cs and Sr, to the power of ?2 in the presence of PEG, whereas in the PEG-free systems the dependences are nonlinear. The synergistic extractant is characterized by higher (by an order of magnitude) solubility of metal solvates as compared to the HDBP-MNBTF system (concentration of Eu in the extractant >0.163 M). The extractant containing HDBP (1.1 M), CCD (0.23 M), and Slovafol-90 (0.065 M) in MNBTF is suggested for combined recovery of rareearth (REE) and transplutonium elements (TPE) and of Cs and Sr from high-level waste (HLW) after reprocessing of spent nuclear fuel (SNF) with high burn-up.     

Sorption of long-lived radionuclides onto main types of rocks of the Novaya Zemlya Archipelago

The ability of black carbonaceous siltstones and silt sandstones, lime sandstones, gray limestones, carbon–silicon carbonate schists with pyrite, and other rocks that most widely occur on the Novaya Zemlya Archipelago to sorb ¹³⁷Cs, ⁹⁰Sr, ^239+240Pu, and ²⁴¹Am was studied. The distribution coefficients K _d (cm³ g^–1) are as follows: for ^239+240Pu, 2.7 × 10³–7.7 × 10³; for 241Am, 2.5 × 10³–1.8 × 10⁴; and for ¹³⁷Cs, 1.1 × 10²–2.0 × 10³. Strontium-85(90) it not noticeably sorbed (within the measurement uncertainty) by any of the rocks studied. ^239+240Pu, ²⁴¹Am, and ¹³⁷Cs are strongly sorbed onto the rocks studied and are not noticeably desorbed from them with distilled water. The data obtained are required for predicting the migration of long-lived radionuclides generated by nuclear explosion with surface waters from test sites on the Novaya Zemlya Archipelago.     

Effect of bioactive dental adhesive on periodontal and endodontic pathogens

The objectives of this study were to: (1) develop a new bioactive dental bonding agent with nanoparticles of amorphous calcium phosphate and dimethylaminohexadecyl methacrylate for tooth root caries restorations and endodontic applications, and (2) investigate biofilm inhibition by the bioactive bonding agent against eight species of periodontal and endodontic pathogens for the first time. Bonding agent was formulated with 5?% of dimethylaminohexadecyl methacrylate. Nanoparticles of amorphous calcium phosphate at 30?wt% was mixed into adhesive. Eight species of biofilms were grown on resins: Porphyromonas gingivalis, Prevotella intermedia, Prevotella nigrescens, Aggregatibacter actinomycetemcomitans, Fusobacterium nucleatum, Parvimonas micra, Enterococcus faecalis, Enterococcus faecium. Colony-forming units, live/dead assay, biomass, metabolic activity and polysaccharide of biofilms were determined. The results showed that adding dimethylaminohexadecyl methacrylate and nanoparticles of amorphous calcium phosphate into bonding agent did not decrease dentin bond strength (P?>?0.1). Adding dimethylaminohexadecyl methacrylate reduced the colony-forming units of all eight species of biofilms by nearly three orders of magnitude. The killing efficacy of dimethylaminohexadecyl methacrylate resin was: P. gingivalis?>?A. actinomycetemcomitans?>?P. intermedia?>?P. nigrescens?>?F. nucleatum?>?P. micra?>?E. faecalis?>?E. faecium. Dimethylaminohexadecyl methacrylate resin had much less biomass, metabolic activity and polysaccharide of biofilms than those without dimethylaminohexadecyl methacrylate (P?<?0.05). In conclusion, a novel dental adhesive was developed for root caries and endodontic applications, showing potent inhibition of biofilms of eight species of periodontal and endodontic pathogens, and reducing colony-forming units by three orders of magnitude. The bioactive adhesive is promising for tooth root restorations to provide subgingival margins with anti-periodontal pathogen capabilities, and for endodontic sealer applications to combat endodontic biofilms.     

Synthesis of New Crystalline Pu(V) Compounds from Solutions: II. Double Pu(V) Oxalates with Co(NH<Subscript>3</Subscript>)<Subscript>6</Subscript><Superscript>3+</Superscript> Ions in the Outer Sphere

Crystalline compounds of the general composition Co(NH³)⁶PuO₂(C₂O₄)²·nH₂O (n = 2, 3, 5) were isolated from freshly prepared neutral oxalate solutions of Pu(V) by addition of Co(NH₃)₆³⁺ ions. These compounds are fairly stable in storage in air and poorly soluble in water. Previously unknown double Np(V) oxalates Co(NH₃)₆NpO₂(C₂O₄)·nH₂O (n = 2, 5) were also synthesized and studied. All the compounds of Pu(V) and Np(V) of the same composition are mutually isostructural. The behavior of these compounds at heating was studied, and their IR spectra were measured. The optical spectra of new Np(V) compounds were measured.     

Interaction of neptunium and technetium with UO<Subscript>2+<Emphasis Type="Italic">x</Emphasis></Subscript>

Interaction of uranium dioxide with highly mobile radionuclides ²³⁷Np and ⁹⁹Tc was studied under oxidative conditions. Sorption of these radionuclides at different pH was measured, and the mechanism of redox reaction occurring in the course of their sorption were determined. In alkaline solution, Np(V) is reduced on the UO_2+x surface and is sorbed in the form of tetravalent species. In neutral solutions, Np is sorbed in the form of Np(V). This is due to the fact that the stoichiometry of the UO_2+x surface corresponds to U₄O₉. In acid solution, U(VI) is leached to form surface UO₂. Although the free surface area of a UO_2+x sample is low, the Np distribution coefficients K _d at pH > 6 are relatively high: log K _d > 2. Unlike Np, Tc(VII) is not reduced on the UO_2+x surface. However, the sorption capacity of uranium dioxide for Tc(IV) is high.     

Effect of the Structure of <Emphasis Type="Italic">o</Emphasis>-Methyleneoxyphenyldiphosphine Dioxides on Their Extractive Power and Selectivity in Nitric Acid Solutions

Extraction of trace amounts of Pu(IV), U(VI), Th(IV), Am(III), and REEs(III) from nitric acid solutions with o-methyleneoxyphenyldiphosphine dioxides with phenyl (I) and butyl (II) substituents at the phosphoryl group is studied. The stoichiometry of extractable complexes in dichloroethane is determined. Changing the butyl substituents for phenyl ones increases the effective extraction constants of Pu(IV), Th(IV), and Am(III) and decreases that of U(VI). In extraction from 3 M HNO³, the Pu(IV)/U(VI) and Th(IV)/U(VI) partition coefficients are higher with reagent I, and the Pu(IV)/Am(III) and U(VI)/Am(III) partition coefficients, with reagent II.     

Recovery of Np(V), Pu(IV), and Am(III) by solid-phase extraction with supported <Emphasis Type="Italic">N</Emphasis>-benzoylphenylhydroxylamine

Recovery of Np(V), Pu(IV), and Am(III) by solid-phase extraction with supported N-benzoylphenylhydroxylamine (BPHA) from simulated groundwater with pH 8.5 was studied. DIAPAK C16 cartridges modified with BPHA can be used for preconcentration of these elements from natural waters by solid-phase extraction.     

Synthesis of M(NpO<Subscript>4</Subscript>)<Subscript>2</Subscript>·<Emphasis Type="Italic">n</Emphasis>H<Subscript>2</Subscript>O (M = Mg,Ca, Sr,Ba) Using Н<Subscript>3</Subscript>ВО<Subscript>3</Subscript> Solutions and Properties of These Salts

Two procedures for preparing the compounds M(NpO₄)₂·nH₂O (M = Mg, Ca, Sr, Ba) using boric acid were suggested. In the first procedure, samples of freshly prepared salts M₃(NpO₅)₂·nH₂O (M = Ca, Sr, Ba) are treated with excess 0.5 M H₃BO₃ with vigorous stirring. In the process, the initially light green salts rapidly transform into black products of the general composition M(NpO₄)₂·nH₂O. In the second procedure, a measured volume of a Np(VII) solution with a known LiOH concentration was added to excess 0.5 M H3BO3 solution containing a calculated amount of Mg, Ca, Sr, or Ba nitrate. The reaction yields black precipitates of the same compounds as in the previous case. After washing with water and drying in an oxygen stream, the final products contain a small impurity of Np(VI). The IR spectra suggest that the compounds obtained are structurally related to the previously studied salts MNpO₄ (M = K–Cs), i.e., in their lattices there are neptunium–oxygen layers built of NpO₂³⁺ cations and bridging O atoms. New data on the properties of the compounds M₃(NpO₅)₂·nH₂O with M = Ca, Sr, and Ba were also obtained.     

Stereochemistry of Plutonium in Oxygen-Containing Compounds

The coordination of 122 crystallographically nonequivalent Pu(III, IV, V, VI, VII) atoms in the crystal structures of all the oxygen-containing compounds characterized with the R-factor lower than 0.1 was analyzed with the aid of Voronoi–Dirichlet polyhedra (VDPs). The Pu atoms form PuO _n coordination polyhedra (6 ≤ n ≤ 12) of 14 types. At a fixed oxidation state of the Pu atoms, the plutonium VDP volume in PuO _n complexes is virtually independent of the coordination number n. The rule of 14 neighbors is fulfilled in sublattices consisting of Pu atoms (Pu sublattices). Analysis of the PVD characteristics in Pu sublattices revealed compounds in which the occurrence of bonding Pu–Pu 5f interactions can be assumed. As demonstrated by the example of Pu(III), the VDP parameters can be successfully used for finding the most adequate 4f surrogates for highly radioactive transuranium elements.     

Effect of Charge Reservoir Layer on the Structural and Transport Properties of CuTlBa<Subscript>2−Y</Subscript>Sr<Subscript><Emphasis Type="Italic">Y</Emphasis></Subscript>-1223 (<Emphasis Type="Italic">Y</Emphasis> = 0 − 0.25) Superconductor

The bulk superconducting composites Cu_0.5Tl_0.5 Ba_2?YSr _Y Ca₂Cu₃O₁0?δ (Y = 0, 0.15, and 0.25) have been synthesized at an ambient pressure. The techniques used to characterize the samples were X-ray scans, Fourier transform infrared spectroscopy (FTIR), and dc resistivity (ρ) measurements. In CuTl-1223 system, we replaced Sr atom at Ba site and studied the superconducting properties of squeezed charge reservoir layer (CRL). From the XRD analysis, it is confirmed that the samples have orthorhombic structure and the dimensional parameters of the unit cell suppressed with the dopant atom which is most probably due to small in size of Sr atom as compared with Ba. The normal-state resistivity and critical temperatures, i.e., T _c (R = 0) and \(T_{\mathrm {c}}^{\text {onset}}\) are observed to be suppressed. The lower values of critical temperature T _c (R = 0) and activation energy U _o (eV) might be possible due to a weak flux pinning. Accordingly, a reduction of weak links and enhanced insulating nature of inter-grain coupling were observed with the doping of Sr atom in CRL. Moreover, the doping in CRL of Sr atom is also confirmed with the FTIR technique. The intrinsic parameters, i.e., coherence length ξ _c(0), crossover temperatures (T _3D?2D), inter-layer coupling (J), etc. were calculated by fluctuation-induced conductivity (FIC) analysis.     

New approaches to reprocessing of oxide nuclear fuel

Dissolution of UO₂, U₃O₈, and solid solutions of actinides in UO₂, including those containing Cs, Sr, and Tc, in weakly acidic (pH 0.9–1.4) aqueous solutions of Fe(III) nitrate or chloride was studied. Complete dissolution of the oxides is attained at a molar ratio of Fe(III) nitrate or chloride to uranium of 1.6 or 2.0, respectively. In the process, actinides pass into the solution in the form of U(VI), Np(V), Pu(III), and Am(III). At 60°C, actinide oxides dissolve in these media faster than at room temperature. In the solutions obtained, U(VI) and Pu(III) are stable both at room temperature and at elevated temperatures (60°C), and also at high U concentrations (up to 300 mg ml⁻¹) typical of process solutions (6–8 M HNO₃, ∼60–80°C). After the oxide fuel dissolution, U and Pu are recovered from the solution by peroxide precipitation. In so doing, the content of Fe, Tc, Cs, and Sr in the precipitate does not exceed ∼0.05 wt %. From the solution after the U and Pu separation, the fission lanthanides, Tc, Cs, and Sr can be recovered by precipitation of Fe hydroxides in the presence of ferrocyanide ions and can be immobilized in appropriate matrices suitable for long-term and environmentally safe storage.     

Synthesis,crystal structure,and properties of new actinide(VI) arsenates (H<Subscript>3</Subscript>O)[(AnO<Subscript>2</Subscript>)(AsO<Subscript>4</Subscript>)]·3H<Subscript>2</Subscript>O (An = U,Np, Pu)

Previously unknown arsenates of hexavalent U, Np, and Pu, (H₃O)[(UO₂)(AsO₄)]·3H₂O (I), (H₃O)· [(NpO₂)(AsO₄)]·3H₂O (II), and (H₃O)[(PuO₂)(AsO₄)]·3H₂O (III), were synthesized under hydrothermal conditions. The crystal structure of the compounds was determined, and their absorption spectra were measured. The compounds crystallize in tetragonal space group P4/nmm.