Affinity and removal of radionuclides mixture from low-level liquid waste by synthetic ferrierites

The affinity and removal efficiency of ¹³⁷Cs⁺, ¹³³Ba²⁺, ⁸⁵Sr²⁺ and ²⁴¹Am³⁺ mixture from aqueous solutions using two synthetic ferrierites HSZ 700KOA and 700KOD commercially used as a catalyst in oil industry were investigated. The uptake of metal ions as a function of different parameters has been studied using batch equilibrium technique. Kinetic curves showed that the equilibrium was mostly reached within 45 min for Cs⁺ and Ba²⁺ and revealed to be longer for Sr²⁺ and Am³⁺. Using Freundlich and Langmuir adsorption isotherms, the results showed that the affinity and adsorption capacity of 700KOA and 700KOD follow the order: Cs⁺ > Ba²⁺ > Sr²⁺ > Am³⁺ with higher values for first material. Both adsorbents exhibited significant high capacity for Cs⁺ relative to other cations giving q _max 1.97 and 1.78 mmol g⁻¹ for 700KOA and 700KOD, respectively. All metals uptake found to be concentration dependant and independent of the pH over 2 to 10 range except Am³⁺; this reveals that the adsorption mechanism is controlled mainly by pure ion exchange reaction for Cs⁺, Ba²⁺, Sr²⁺ and by surface complexation mechanism for Am³⁺. These simple nontoxic materials are recommended to be used for radioactive waste treatment especially fission product ¹³⁷Cs and activation product ¹³³Ba.     

Extraction of actinides and fission products from salt solutions using polyethylene glycols (PEGs)

The extraction behavior of several metal ions viz., Am³⁺, Eu³⁺, UO₂ ²⁺, Th⁴⁺, Sr²⁺ and Cs⁺ was investigated from sulphate medium employing phosphotungstic acid (PTA) and polyethylene glycol (PEG). The influence of various parameters such as pH, PTA concentration, PEG concentration and salt concentration was studied. The order of extraction followed the trend: Am³⁺>Eu³⁺>>Th⁴⁺>UO₂ ²⁺>Sr²⁺>Cs⁺ which deviate significantly from the reported order with conventional solvents. The relatively poor extraction of UO₂ ²⁺, Sr²⁺ and Cs⁺ was ascribed to their lack of interaction with the phosphotungstate anion. The separation behaviour of Am³⁺ vis-a-vis Eu³⁺ was also investigated under different experimental conditions.     

Preparation of AmIV and AmVI in bicarbonate and carbonate solutions using xenon compounds

Xe compounds, XeF₂, Na₄XeO₆, and XeO₃, were used to oxidize Am^III in carbonate and bicarbonate aqueous solutions. XeF₂ and XeO₃ may be used to obtain Am^IV in solutions, whereas Na₄XeO₆ oxidizes Am^III into Am^IV+An^V+Am^VI or into Am^VI if present in excess. XeO³ reacts with Am^III to give Am^IV only under UV irradiation.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 953–954, May, 1994.     

Solvent Extraction of Calcium and Strontium into Nitrobenzene by Using Hydrogen Dicarbollylcobaltate in the Presence of Dibutyl Diethylcarbamoylmethylene Phosphonate

Extraction of micro amounts of calcium and strontium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H⁺B⁻) in the presence of dibutyl diethylcarbamoylmethylene phosphonate (DBDECMP, L) has been investigated. The equilibrium data have been explained assuming that the complexes HL⁺, HL₂⁺\mathrm{HL}_{2}^{+}, ML₂²⁺\mathrm{ML}_{2}^{2+} and ML₃²⁺\mathrm{ML}_{3}^{2+} (M²⁺=Ca²⁺,Sr²⁺) are extracted into the organic phase. The values of extraction and stability constants of the species in nitrobenzene saturated with water have been determined. It was found that the stability of the complex cations CaL₃²⁺\mathrm{CaL}_{3}^{2+}, SrL₃²⁺\mathrm{SrL}_{3}^{2+}, EuL₃³⁺\mathrm{EuL}_{3}^{3+} and AmL₃³⁺\mathrm{AmL}_{3}^{3+}, where L is DBDECMP, increases in the order Sr²⁺<Ca²⁺≪Eu³⁺≈Am³⁺.     

Pore-functionalized polymer membranes for preconcentration of heavy metal ions

Functionalized membranes containing carboxylate, phosphate and sulfonate groups were prepared by UV-initiator induced graft polymerization of the functional monomer (acrylic acid, ethylene glycol methacrylate phosphate (EGMP) and 2-acrylamido-2-methyl-1-propane sulfonic acid) with a crosslinker (methylenebisacrylamide) in the pores of poly(propylene) host membranes. The functionalized membranes thus obtained were characterized by gravimetry, FTIR spectroscopy, radiotracers and scanning electron microscopy for the degree of grafting and water uptake, presence of functional groups, ion-exchange capacity, and physical structure of the membranes, respectively. The uptakes of Cs⁺, Ag⁺, Sr²⁺, Cd²⁺, Hg²⁺, Zn²⁺, Eu³⁺, Am³⁺, Hf⁴⁺ and Pu⁴⁺ ions in the functionalized membranes were studied as a function of acidity of the equilibrating aqueous solution. Among the functionalized membranes prepared in the present work, the EGMP-grafted membrane (with phosphate groups) showed acid concentration dependent selectivity towards multivalent metal ions like Eu³⁺, Am³⁺, Hf⁴⁺ and Pu⁴⁺. The solvent extraction studies of EGMP monomer in methyl isobutyl ketone (MIBK) solvent indicated that divalent and trivalent metal ions form complexes with EGMP in 1:2 proportion, but the distribution coefficients of trivalent metal ions were significantly higher that for the divalent ions. The uptakes of Eu³⁺ ions in monomeric EGMP (dissolved in MIBK) and polymeric EGMP (in the forms of crosslinked gel and membrane) were studied as a function of concentration of H⁺ ions in the equilibrating solution. This study indicated that polymeric EGMP has better binding ability towards Eu³⁺ as compared to monomeric EGMP. The variation of distribution coefficients of Eu³⁺/Am³⁺ in gel and membrane as a function of H⁺ ion concentration in the equilibrating aqueous solution indicated that ionic species held in the membrane and gel were not same. These results indicated that proximity of functional groups (phosphate) plays an important role in metal ion binding with polymeric EGMP.     

Synergistic extraction of europium and americium into nitrobenzene by using hydrogen dicarbollylcobaltate and 1,2-(diphenylphosphino)ethane dioxide

Extraction of microamounts of europium and americium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H⁺B⁻) in the presence of 1,2-(diphenylphosphino)ethane dioxide (DPPEtDO, L) has been investigated. The equilibrium data have been explained assuming that the species HL⁺, HL₂ ⁺, ML₂ ³⁺ and ML₄ ³⁺ (M³⁺ = Eu³⁺, Am³⁺) are extracted into the organic phase. The values of extraction and stability constants of the species in nitrobenzene saturated with water have been determined. It was found that the stability constants of the corresponding complexes EuL _n ³⁺ and AmL _n ³⁺, where n = 2, 4 and L is DPPEtDO, in water-saturated nitrobenzene are comparable.     

Three Alginate Lyases from Marine Bacterium <Emphasis Type="Italic">Pseudomonas fluorescens</Emphasis> HZJ216: Purification and Characterization

Three alginate lyases (A, B, and C) from an alginate-degrading marine bacterium strain HZJ216 isolated from brown seaweed in the Yellow Sea of China and identified preliminarily as Pseudomonas fluorescens are purified, and their biochemical properties are described. Molecular masses of the three enzymes are determined by SDS-PAGE to be 60.25, 36, and 23 kDa with isoelectric points of 4, 4.36, and 4.59, respectively. Investigations of these enzymes at different pH and temperatures show that they are most active at pH 7.0 and 35 °C. Alginate lyases A and B are stable in the pH range of 5.0–9.0, while alginate lyase C is stable in the pH range of 5.0–7.0. Among the metal ions tested, additions of Na⁺, K⁺, and Mg²⁺ ions can enhance the enzyme activities while Fe²⁺, Fe³⁺, Ba²⁺, and Zn²⁺ ions show inhibitory effects. The substrate specificity results demonstrate that alginate lyase C has the specificity for G block while alginate lyases A and B have the activities for both M and G blocks. It is the first report about extracellular alginate lyases with high alginate-degrading activity from P. fluorescens.     

Solvent extraction of europium and americium into phenyltrifluoromethyl sulfone by using synergistic mixture of hydrogen dicarbollylcobaltate and “classical” CMPO

Extraction of microamounts of europium and americium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H⁺B⁻) in the presence of tetraisopropyl methylene diphosphonate [T(iPr)MDP, L] has been investigated. The equilibrium data have been explained assuming that the complexes HL⁺, HL₂ ⁺, ML₂ ³⁺, ML₃ ³⁺ and ML₄ ³⁺ (M³⁺ = Eu³⁺, Am³⁺) are extracted into the organic phase. The values of extraction and stability constants of the species in nitrobenzene saturated with water have been determined. It was found that the stability constants of the corresponding complexes EuL _n ³⁺ and AmL _n ³⁺, where n = 2, 3, 4 and L is T(iPr)MDP, in water-saturated nitrobenzene are comparable.     

Thermodynamic modeling of actinide complexation with oxalate at high ionic strength

A geochemical model describing the solubility of actinides in underground water at the Waste Isolation Pilot Plant (WIPP) Project is under development. The database for this model consists of standard chemical potentials and Pitzer model parameters for hundreds of species that may be present in the WIPP disposal room. Organic ligands used in separation and decontamination processes may be present in the nuclear wastes placed in the WIPP site and could have a significant impact on mobile actinide concentrations. In this work the ₁ and ₂ stability constants of NpO₂ ⁺, UO₂ ²⁺, Am³⁺ and Th⁴⁺ with the oxalate anion have been measured in 0.3–5.0M NaCl media at 25 °C by a solvent extraction technique. For the 1:1 complexation, the values of the stability constants increased in the order: NpO₂ ⁺<Am³⁺<UO₂ ²⁺<Th⁴⁺, in accordance with the actinide charge density and reflecting the strongly ionic bonding of the complexes. The Pitzer ionic interaction model was used to model the data. Because the data were collected mainly in the high ionic strength region, values of ⁽¹⁾ were estimated from these plus literature values. The Pitzer model gives a good representation of the data using three interaction parameters ⁽⁰⁾, ⁽¹⁾, and c.     

Extraction of microamounts of europium and americium by using hydrogen dicarbollylcobaltate in the presence of dibutyl diethylcarbamoylmethylene phosphonate

Extraction of microamounts of europium and americium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H⁺B⁻) in the presence of dibutyl diethylcarbamoylmethylene phosphonate (DBDECMP, L) has been investigated. The equilibrium data have been explained assuming that the complexes HL⁺, HL₂²⁺ ML₃³⁺ and ML₄³⁺ (M³⁺ = Eu³⁺, Am³⁺) are extracted into the organic phase. The values of extraction and stability constants of the species in nitrobenzene saturated with water have been determined.     

Interaction of actinide ions with [NaP5W30O110]14- and [P2W18O62]6-

Stability constants (log b₁₀₁) of Th⁴⁺, UO₂ ²⁺, NpO₂ ⁺ and Am³⁺ with [NaP₅W₃₀O₁₁₀]^14- were determined by solvent extraction (m = 0.1M NaCl) and found to be 6.18±0.07, 3.80±0.06, 2.98±0.04, and 5.85±0.05, respectively. The order of stability constants: Th⁴⁺>Am³⁺>UO₂ ²⁺>NpO₂ ⁺ is due to electrostatic repulsion between the actinyl oxygens and oxygens on the polyoxometalate surface. The order of stability constants for metal complexes with [P₂W₁₈O₆₂]^6- is Th⁴⁺>UO₂ ²⁺>Eu³⁺>NpO₂ ⁺ because the steric repulsion between actinyl oxygens and oxygens on polyoxometalate are less important. Enthalpies of complexation were measured by calorimetric titration of Th⁴⁺, UO₂ ²⁺, Nd³⁺ with [NaP₅W₃₀O₁₁₀]^14- and [P₂W₁₈O₆₂]^6-. The results indicate that the conformation and charge distribution of the microscopic surface structures are important factors in the formation of pseudocolloids.     

Autocatalysis by the nitroxyl radical in the cyclic mechanism of chain termination in polymer oxidation

The activation energy and rate constant of the reaction between the nitroxyl radical and N-alkoxyamine as a concerted abstraction–fragmentation reaction have been calculated using the intersecting parabolas model. This reaction proceeds fairly rapidly and leads to nitroxyl radical autoregeneration as a result of the following consecutive reactions:AmO^? + AmOR → AmOH + >C=O + Am^?, RO ₂ ^? + AmOH → ROOH + AmO^?, Am^?+ O₂ → Am ₂ ^? , and 2AmO ₂ ^? → 2AmO^? + O₂. Thus, the nitroxyl radical is an effective radical catalyst for its own regeneration from N-alkoxyamine. The rates of regeneration of the nitroxyl radical from its N-alkoxyamine under the action of alkyl, alkoxyl, peroxyl, nitroxyl, and hydroperoxyl radicals under conditions of polypropylene oxidation inhibited by the nitroxyl radical are compared. It is demonstrated that only peroxyl, hydroperoxyl, and nitroxyl radicals are involved in AmO^? regeneration from AmOR.     

Extraction of microamounts of europium and americium into nitrobenzene by using hydrogen dicarbollylcobaltate in the presence of diphenyl-N-butylcarbamoylmethyl phosphine oxide

Extraction of microamounts of europium and americium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H⁺B⁻) in the presence of diphenyl-N-butylcarbamoylmethyl phosphine oxide (DPBCMPO, L) has been investigated. The equilibrium data have been explained assuming that the complexes HL⁺, HL₂⁺, ML₂³⁺, ML₃³⁺ and ML₄³⁺ (M³⁺ = Eu³⁺, Am³⁺) are extracted into the organic phase. The values of extraction and stability constants of the species in nitrobenzene saturated with water have been determined. It has been found that the stability constants of the corresponding complexes EuL _n ³⁺ and AmL _n ³⁺, where n = 2, 3, 4 and L is DPBCMPO, in water saturated nitrobenzene are comparable.     

Coordination of Actinide Single Ions to Deformed Graphdiyne: Strategy on Essential Separation Processes in Nuclear Fuel Cycle

The coordination of actinides and lanthanides, as well as strontium and cesium with graphdiyne (GDY) was studied experimentally and theoretically. On the basis of experimental results and/or theoretical calculations, it was suggested that Th⁴⁺, Pu⁴⁺, Am³⁺, Cm³⁺, and Cs⁺ exist in single‐ion states on the special triangular structure of GDY with various coordination patterns, wherein GDY itself is deformed in different ways. Both experiment and theoretical calculations strongly indicate that UO₂²⁺, La³⁺, Eu³⁺, Tm³⁺ and Sr²⁺ are not adsorbed by GDY at all. The distinguished adsorption behaviors of GDY afford an important strategy for highly selective separation of actinides and lanthanides, Th⁴⁺ and UO₂²⁺, and Cs⁺ and Sr²⁺, in the nuclear fuel cycle. Also, the present work sheds light on an approach to explore the unique functions and physicochemical properties of actinides in single‐ion states.     

Extractive distribution of microamounts of europium and americium in the two phase water — HCl — nitrobenzene — N,N,N′,N′-tetraethyl-2,6-dipicolinamide — hydrogen dicarbollylcobaltate system

Extraction of microamounts of europium and americium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H⁺B⁻) in the presence of N,N,N′,N′-tetraethyl-2,6-dipicolinamide (TEtDPA, L) has been investigated. The equilibrium data have been explained assuming that the cations HL⁺, HL₂³⁺, ML₂³⁺ and ML₃³⁺ (M³⁺ = Eu³⁺, Am³⁺) are extracted into the organic phase. The values of extraction and stability constants of the species in nitrobenzene saturated with water have been determined. It has been found that the stability constants of the corresponding complexes EuL _n,org³⁺ and AmL _n,org³⁺, where n = 2, 3 and L is TEtDPA, in the mentioned medium are comparable.     

Efficiency of a fixed-bed and a gas-lift three-column reactor for continuous production of ethanol by pectate-and alginate-immobilized Saccharomyces cerevisiae cells

Ethanol-tolerant and thermo-tolerant yeast strain Saccharomyces cerevisiae C11-3 cells immobilized in calcium pectate and calcium alginate gels were used for ethanol fermentation in a three-reactor system with a gradient temperature control. The fermentation process has been tested in a fixed-bed and a gas-lift arrangement. The gas-lift system was more efficient due to a better mass transport between the phases. Abrasion was more evident in calcium alginate particles, while calcium pectate beads were not significantly damaged. Two different concentrations of alginate were tested and calcium pectate gel was demonstrated to be more suitable as an immobilization material in comparison with calcium alginate due to its mechanical resistance and favourable diffusion parameters, providing an ethanol production of more than 7.5 g dm⁻³ h⁻¹ over a period of 630 h.     

Solvent extraction of calcium and strontium into nitrobenzene by using hydrogen dicarbollylcobaltate in the presence of polypropylene glycol PPG 425

From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibrium M⁺(aq) + Cs⁺(org) ⟺ M⁺(org) + Cs⁺(aq) taking place in the two-phase water–phenyltrifluoromethyl sulfone (abbrev. FS 13) system (M⁺ = Li⁺, H₃O⁺, Na⁺, NH₄⁺ \hbox{NH}_{4}{}^{+} , Ag⁺, Tl⁺, K⁺, Rb⁺; aq = aqueous phase, org = FS 13 phase) were evaluated. Furthermore, the individual extraction constants of the M⁺ cations in the mentioned two-phase system were calculated; they were found to increase in the series of Li⁺ < H₃O⁺ < Na⁺< NH₄ ⁺ \hbox{NH}_{4}{}^{ + } < Ag⁺ < Tl⁺ < K⁺ < Rb⁺ < Cs⁺.     

On the metal ion selectivity of PNP-lariat ether—an insight from density functional theory calculations

The complexes of Li⁺, Na⁺, K⁺, Be²⁺, Mg²⁺, and Ca²⁺ metal cations with [N₃P₃R₄O(CH₂CH₂O)₄] (R?=?H(1), NMe₂(2), NC(NMe₂)₂(3)) PNP-lariat ethers were systematically studied in the gas phase by using density functional theory (DFT) B3LYP-D3/6-311+G(3df,2p)//B3LYP/6-31+G(d,p) method. The gas phase cation affinities were calculated to span the wide range between 64.2 and 496.1 kcal mol^?1 in order K⁺?<?Na⁺?<?Li⁺?<?Ca²⁺?<?Mg²⁺?<?Be²⁺. The structural and electronic properties of 1–3 and their complexes were investigated and effects of electron-donor substituents were analyzed. The electron-donor substituents were found to promote the cation affinity. Sidearm coordinative interaction with the crown ether-complexed metal ion has been noticed. The nature of the metal–ligand interactions was investigated using Bader’s Quantum theory of atoms in molecule. It has been found that the Be²⁺–N bonds are partly covalent in nature while other coordinate bonds are of the electrostatic nature. The electron density at the bond critical points was found to be consistent with cation affinity. Natural bond orbital analysis was performed on the optimized geometries. The results showed that the stabilization interaction energies are caused by the donation of O/N lone pair electrons to the LP* orbitals of the metal cations. The amount of charge transfer follows the cation affinity order. The largest charge transfer and associated second-order perturbation stabilization energy were observed for Be²⁺ complexes.

     

Binding of some first-row transition metal ions by a poly(iminoethylene)dithiocarbamate copolymer

The binding of the transition metal ions VO²⁺, Fe²⁺, Fe³⁺, CO²⁺, Co³⁺, Ni²⁺ and Cu²⁺ by a poly(iminoethylene) dithiocarbamate copolymer has been investigated by uptake studies and physical measurements (electronic, IR, and ESR spectra and magnetic susceptibility). Metal ions may be bound by both the dithiocarbamato and amino groups of the co-polymer. Binding to nitrogen (in addition to binding to sulphur) increases in the order FE(II)<Ni(II)<Cu(II) and accounted for increasing metal ion uptake by the copolymer in the same order. Factors which determine the relative uptake of the metal ions by the copolymer are discussed.     

Extraction chromatographic study on the separation of Am<Superscript>3+</Superscript> and Eu<Superscript>3+</Superscript> using ethyl-BTP as the extractant

Ethyl-substituted bis-triazinylpyridine (Et-BTP), a nitrogen containing soft-donor extractant, was used in investigations pertaining to the separation of Am³⁺ and Eu³⁺ from dilute nitric acid feed solutions by extraction chromatography using XAD-4 as the inert support, chlorinated dicarbollide as the modifier and 2-nitrophenyloctylether (NPOE) as the diluent. After carrying out a series of experiments, the optimum composition of the extractant mixture for the resin was found out to be 0.1 M Et-BTP and 0.025 M CCD in NPOE. Separation factor values were encouraging to carry out subsequent batch uptake studies at varying nitrate ion concentration which indicated favourable separation behaviour up to NaNO₃ concentration of 2 M. Column studies have been carried out and conditions for elution and separation of Am³⁺ from Eu³⁺ have been found out. Long term stability of the resin was also investigated.