Determination of alpha-emitting isotopes in radioactive wastes

An analytical procedure was developed for the alpha-spectrometric determination of uranium (²³⁸U, ²³⁵U, ²³⁴U) and transuranium isotopes (^239+240Pu, ²⁴⁴Cm) in liquid radioactive wastes (sludges, evaporation residues) of low and medium activity from the VVER-440 reactor of the nuclear power plant in Paks, and in waste waters to be released into the environment. Radioactive sludge samples were separated to a liquid phase and a wet suspension (solid) phase by centrifuging, and the two phases were treated and analyzed separately, in different ways. A sample preparation procedure based on chemical separation was worked out for the isolation of the alpha-emitting components of radioactive evaporation residues which were saturated with boric acid. To the separate determination of the low activity alpha-emitting isotopes appearing in waste waters to be released into the environment, a microvawe concentration technique was applied. The accuracy of the results obtained using the above chemical separation and alpha-spectrometry was tested in the framework of the international U. S. DOE EML Quality Assessment Program.     

Melt densification of radioactive plastic wastes

Summary Volume reduction studies were carried out on low level radioactive plastic wastes containing polyethylene, PVC and neoprene by melt densification. The optimized temperature for melting of plastics was between 170 and 180 °C. Based on laboratory scale studies. Plant scale studies were planned and conducted. The volume reduction factors obtained were around 30, which was 6-10 times higher than that of the conventional compaction process. Thermogravimetry and infrared spectroscopy were used to investigate the thermal and structural properties of the given materials. The effect of the presence of salts like potassium permanganate and hydrazine sulphate on the thermal properties of the materials was also evaluated. Leaching studies were also performed on melt-densified specimens in the laboratory. The average leach index was observed to be around 9, which was higher than the minimum stipulated value.     

Investigations of actinides in the context of final disposal of high-level radioactive waste: trivalent actinides in aqueous solution

The speciation of redox sensitive trivalent actinides Pu(III), Np(III), and U(III) has been studied in aqueous solution. The redox preparation, stabilization, and speciation of these trivalent actinides in aqueous systems are discussed here. The reductants investigated were rongalite, hydroxylamine hydrochloride, and acetohydroxamic acid and the An(III) species have been characterized by UV–Vis and XANES spectroscopy. The results show that the effectiveness of stabilization decreases generally in the order Pu(III) > Np(III) > U(III) and that the effectiveness of each reducing agent depends on the experimental conditions. More than 80 % of Pu(III) aquo species have been stabilized up to pH 5.5, whereas the Np(III) aquo ion could be stabilized in a pH range 0–2.5, and U(III) aquo ion is sufficiently stable at pH 1.0 and below over time periods suitable for experiments. However, this study gives a basis for the characterisation of the trivalent lighter actinides involved in complexation, sorption, and solid formation reactions in the future.     

Analysis of organics in highly radioactive nuclear wastes

Analytical methods are being developed at Pacific Northwest Laboratory (PNL) for the organic analysis of nuclear wastes. In this study our laboratory analyzed the organic content of two highly radioactive wastes, a neutralized cladding removal waste (NCRW) and a volume reduction, double-shell slurry (DSS) waste. In-house methods were developed and U.S. Environmental Protection Agency (EPA) methods were modified for isolating and analyzing volatile, semivolatile and hydrophilic organics in the hot cell and radiation hood. The procedures worked well, particularly for the NCRW, in which 94.9% of the waste's total organic carbon (TOC) has been characterized. In contrast, only 1.2% of the DSS waste's TOC has been identified to date. Quite a variety of volatile, semivolatile and hydrophilic organics, e.g., chelating agents, were identified in the wastes, occasionally at relatively high mM, or mg/g, concentrations. Most of the compounds are either source-term organics associated with nuclear operations or their degradation products, indicating that organic diagenesis in nuclear wastes can be quite vigorous and extensive.     

Radiological characterization of low-and intermediate-level radioactive wastes

An analytical procedure for the determination of activation products ²³⁸Pu, ²⁴¹Pu, ²³⁹Pu/²⁴⁰Pu, ²⁴¹Am, ²³⁷Np, and a fission product ⁹⁰Sr in radioactive wastes is presented. Samples were decomposed using Fenton’s reaction. The separation was performed by anion-exchange chromatography, extraction chromatography, using TRU and Srresin, and precipitation techniques, followed by α-spectrometry and LSC counting. Tracer solutions and pure ion exchange resins were used to prepare artificial samples and trace nuclides during the analytical procedure. Some real samples of spent ion-exchange resins originating from our TRIGA Mark II research reactor were analyzed.     

Extraction of actinides from simulated HLLW by DHDECMP-TBP/OK

The partitioning of actinides from simulated high level liquid waste (HLLW) originated from the Purex process has been studied using a mixture of dihexyl N,N-diethylcarbamoylmethyl-phosphonate (DHDECMP) and tributylphosphonate (TBP) in kerosene (OK). The distribution ratios of actinides were investigated as a function of a number of parameters such as the concentration of nitric acid, salting-out reagent, Gd(III) in the aqueous phase, extractant in the organic phase, and temperature. The extraction complexes, extraction reaction constant k, and thermodynamic parameters H, G and S were determined. The extraction of actinides from simulated HLLW by DHDECMP-TBP/OK has been carried out using a miniature countercurrent centrifugal contactor. The results show that the removal efficiency of actinides is greater than 99.9%. A conceptual flowsheet for the removal of actinides from HLLW is proposed.This revised version was published online in November 2005 with corrections to the Cover Date.     

Denitration of simulated radioactive liquid waste

Journal of Radioanalytical and Nuclear Chemistry - Radioactive liquid wastes containing large amounts of nitric acid (approx. 4–7 M) generated in the nuclear fuel cycle are very...     

Statistical estimate for evaluation of vitrified radioactive wastes

The evaluation of experimental results by methods of mathematical statistics enabled us to derive a number of conclusions on the leachability of vitrified radioactive wastes. Practical application of this procedure requires that the ratio of Na and K concentrations in the solution should be independent of the leaching time. The actual value of this ratio is influenced, above all, by the properties of the glass matrix. These results confirm the assumption that the Na/K correlation found could be extended for the determination of the Na/¹³⁷ Cs concentration ratio. This finding was used for the application of a In-In correlation, while evaluating the quality of vitrified radioactive wastes products.     

Management of radioactive wastes using a personal computer

This paper describes a software package for a personal computer which deals with storage records of radioactive wastes; the software keeps the records of purchase and use of radioisotopes and makes the inventory records of radioactive wastes. The records for the cargo booking of the wastes for the Japanese Radioisotope Association can be prepared by this software package.     

Decontamination of radioactive liquid wastes by hydrophytic vegetal organisms

This paper deals with the bioaccumulation of some radioactive ions from contaminated waste solutions, on hydrophytic vegetal organisms. In order to follow the distribution of radioactive ions ¹³⁷Cs⁺, ⁶⁰Co²⁺ and ⁵¹Cr³⁺ in various cell components extracted from Spirulina platensis, Porphiridium cruentum, Scenedesmus quadricauda, Lemna minor,Elodea canadensis, Pistia stratiotes and Riccia fluitans, the plants were cultivated in radioactive solutions. The resulting complexes were extracted with acetone or acetic acid and separated chromatographically. The results show an intense activity of the polysaccharide and lipoid fractions in the bioaccumulation process. The bioaccumulation varies in the series: Spirulina>Scenedesmus>Porphiridium>Riccia>Pistia> Lemna ³ Elodea for ¹³⁷Cs⁺ and ⁶⁰Co²⁺; Spirulina>Porphiridium>Scenedesmus>Riccia>Pistia>Lemna>Elodea for ⁵¹Cr³⁺.     

A highly efficient solvent system containing functionalized diglycolamides and an ionic liquid for americium recovery from radioactive wastes

Three room temperature ionic liquids (RTILs), viz. C(4)mim(+)·PF(6)(-), C(6)mim(+)·PF(6)(-) and C(8)mim(+)·PF(6)(-), were evaluated as diluents for the extraction of Am(III) by N,N,N',N'-tetraoctyl diglycolamide (TODGA). At 3 M HNO(3), the D(Am)-values by 0.01 M TODGA were found to be 102, 34 and 74 for C(4)mim(+)·PF(6)(-), C(6)mim(+)·PF(6)(-) and C(8)mim(+)·PF(6)(-), respectively. The extraction of Am(III) decreased with increasing feed acidity for all three diluents, indicating an ion exchange mechanism for the extraction. The stoichiometry of the extracted species suggested that two TODGA molecules were associated with Am(III) during the extraction for all three RTILs and the conditional extraction constants have been determined. The D(M)-values for different metal ions followed the order: 75 (Am(III)) > 30.7 (Pu(IV)) > 3.9 (Np(IV)) > 1.19 (Pu(VI)) > 0.52 (U(VI)) > 0.12 (Cs(I)) > 0.024 (Sr(II)). The distribution behaviour of Am(III) was also studied with a recently synthesized calix[4]arene-4DGA (C4DGA) extractant dissolved in C(8)mim(+)·PF(6)(-). Using this extractant diluent combination, the D(Am)-value was 194 at 3 M HNO(3) using 5 × 10(-5) M C4DGA, suggesting a very high distribution coefficient at very low extractant concentrations. The stoichiometry of the extracted species containing Am was found to be 1:2 (M:L) in C(8)mim(+)·PF(6)(-). The thermodynamics of the extraction was also studied for both extractants in C(8)mim(+)·PF(6)(-). The use of RTILs gives rise to significantly improved extraction properties than the commonly used n-dodecane and an unusual increase in separation factor values was seen for the first time which can lead to selective separation of Am from wastes containing a mixture of U, Pu and Am.     

Determination of technetium-99 in soils and radioactive wastes using ICP-MS

Three methods have been used for the determination of ⁹⁹Tc in soils and solid radioactive wastes using ^99mTc as a yield monitor. In the method one and three the samples were leached in low concentrated nitric and sulphuric acid. Many contaminants were then co-precipitated with Fe(OH)₃ in alkali media and Tc in the supernatant was separated using anion-exchange extraction chromatography. There were made also some studies how to improve the chemical recovery of ^99mTc in the process of chromatography. In the method two the sample was ashed and then leached in 8 mol dm⁻³ HNO₃ and after iron precipitation, technetium was separated on chromatographic column. The chemical recovery of ^99mTc was optimized in the process of chromatography and leaching. Typical recoveries of technetium determined with ^99mTc tracer for all these methods were in the range 39 %–87 %. The ⁹⁹Tc activity was measured using proportional low-background beta detector after one week of staying to allow decay of ^99mTc activity. ⁹⁹Tc was also determined by the non-radiometric method using inductively coupled plasma mass spectrometer.     

Multiconfigurational quantum chemical methods for molecular systems containing actinides

Recent advances in computational actinide chemistry are reported in this tutorial review. Muticonfigurational quantum chemical methods have been employed to study the gas phase spectroscopy of small actinide molecules. Examples of actinide compounds studied in solution are also presented. Finally the multiple bond in the diuranium molecule and other diactinide compounds is described.     

Treatment of simulated liquid radioactive waste containing cobalt by in-situ co-precipitation of Zn/Al layered double hydroxides

Journal of Radioanalytical and Nuclear Chemistry - This paper reports a new approach to treat the cobalt containing wastewater by in situ co-precipitation of Zn/Al layered double hydroxides (LDHs)....     

Separation of boric acid from radioactive wastes by liquid-liquid extraction

The extraction of boric acid from a solution modeling radioactive waste has been studied. Different aliphatic alcohols were used as extractants. Factors affecting the distribution ratio of boric acid and the behaviour of some other components of the solution under conditions of boric acid extraction were investigated. The composition of species extracted was determined from distribution data of n-hexanol and H₃BO₃.     

Treatment of radioactive and industrial liquid wastes by Eichornia crassipes

Chemical factors such as pH, concentration and temperature affecting the removal of UO₂ ²⁺, Th⁴⁺, Fe³⁺, Cu²⁺, Pb²⁺,Cd²⁺, Ni²⁺, MnO₄ ^- and phenol by Eichornia crassipes aquatic plant from their solutions were examined. Maximum uptake of ions by Eichornia crassipes occurred at pH 4 to 6±0.5 at 25±3 °C. An initial rapid uptake phase for the first 6 hours followed by a slower near linear one was observed. One gram of Eichornia crassipes can accumulate about 25 mg UO₂ ²⁺, 5 mg Th⁴⁺, 30 mg Fe³⁺, 10 mg MnO₄ ^-, 15 mg Cu²⁺, 1.0 mg Pb²⁺, 1.5 mg Ni²⁺, 0.7 mg Cd²⁺ and or 25 mg of phenol.     

Diffusion of cyclohexane in native and surface-modified mesoporous glasses

Diffusion of cyclohexane in mesoporous silica materials with different degrees of surface silanization has been probed by means of pulsed field gradient nuclear magnetic resonance. The self-diffusion coefficients have been measured at various pore fillings from about 10% of one monolayer coverage to complete pore saturation by the capillary-condensed phase. It is found that the surface modification, namely grafting of dimethyloctadecylmethoxysilane molecules to the silica surface, reduces diffusivities of guest molecules as compared to the native sample. The contribution of the Knudsen molecular diffusion to the measured diffusivity has been assessed using the model of fast molecular exchange between the adsorbed phase on the pore walls and the molecules in the gaseous phase in the pore interior. The diffusivity data were correlated with the degree of the surface modification, with the latter being probed by measuring ¹H and ¹³C spectra using magic angle spinning (MAS) solid state NMR, nitrogen adsorption and thermogravimetry.     

Activity reduction of radioactive mixed wastes for subsequent carboxylate determinations

Instrumental neutron activation analysis (INAA) based on a nuclear reactor and proton induced X-ray emission (PIXE) based on a 2 Me V Van de Graaff accelerator were used to analyse different environmental samples including coal, sawdust, fly ash and landfill materials. These samples represent a large component of the solid waste being buried in the ground, and may be a potential source of toxicity which can have not only adverse effects on the soil and ground water, if diffused during leaching processes, but may also be transferred to humans through the food chain. Both techniques were employed to determine trace element concentrations in these matrices. The concentration of 30 elements were detemined, namely Na, Mg. Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Cd, Ba, La, Sm, Eu, Tb, Ho, Yb, Hf, Ta and Th. The detection limits in the various sample matrices were calculated and a comparison was made for those elements commonly detected by both techniques.