Hot Test in Mixer Settlers of Alpha Barrier with AHA in PUREX Process

In the PUREX process, the first U-Pu purification cycle (1CUPu) is not efficient enough for the decontamination of uranium flow out of neptunium. In this context, molecules known for their strong complexing power for actinides(IV) in aqueous phase, such as acetohydroxamic acid (AHA) have been tested in batch experiments to strip Np and Pu from TBP solvent loaded with U. A phenomenological model was developed and with the help of this model, a flowsheet of a counter-current alpha barrier process was designed and tested in C17 glove boxes in ATALANTE facility. A decontamination factor DFU/Np of 480 was obtained, higher than DFU/Np required by UNIREP standards.     

The behavior of technetium in technetium-scrubbing stage of PUREX process

Technetium decontamination factor as a function of the acidity, flow ratio, scrubbing stage number was investigated by counter-current cascade experiments or mixer-settler batch tests. Results showed that the acidity of the scrubbing acid has little influence on the decontamination factor of technetium when the acidity was kept in the range of 4.5–6 M. The most effective method to increase the decontamination factor is to lower the feed-to-acid flow ratio. Keeping other condition same the factor increased to 10.3 from 3.1 when feed-to-acid ratio changed to 4 from 5.6. The loss of uranium and plutonium can be recovered through a re-extraction technology.     

The separation of 99Tc from low and medium-level radioactive wastes and its determination by inductively coupled plasma mass spectrometry

A chemical separation method has been developed for the determination of (99)Tc in various types of radioactive wastes. Such a method includes (i) fusion with NaOH, (ii) extraction in a column containing methyltrioctylammonium chloride, (iii) extraction by solvent with N-benzoyl-N-phenylhydroxylamine and, (iv) measurement by inductively-coupled plasma mass spectrometry (ICP-MS). From the performance standpoint, the recovery of (99)Tc, using (99m)Tc as a yield tracer, is higher than 70%. This analytical method, as developed, ensures effective decontamination with respect to the radionuclides, insofar the decontamination factors are greater than 10(+5), whenever the residual activity may be measured. Taking into account a 3sigma counting error, the detection limit obtained with the ICP-MS technique is 1.9 mBq/ml; the method enabling hence to detect activities as low as 0.3 Bq/g, with analysed samples of 0.2 g and a radiochemical yield of 70%. Studies have been dedicated to the (99)Tc measurement, using the electrothermal vaporization ICP-MS technique, which lowers the detection limit by a factor 10, with the standard solution (0.3 pg/ml), compared with the previous ICP-MS technique.     

Comparative study of the corrosion and surface chemical effects of the decontamination technologies

Decontamination technologies are generally developed to reduce the collective dose of the maintenance and operation personnel at nuclear power plants (NPP). The highest efficiency (i.e., the highest decontamination factors) available without detrimental modification of the treated surface of structural material is the most important goal in the course of the application of a decontamination technology. At the Paks NPP the AP-CITROX procedure has been utilized for the decontamination of the primary coolant circuit’s components (e.g., main circulating pump (MCP) and steam generators (SGs)). Our previous studies have revealed that a ‘hybrid’ structure of the amorphous and crystalline phases was formed in the outermost surface region of the austenitic stainless steel tubes of SGs as an undesired consequence of the industrial application of the AP-CITROX decontamination technology during the period of 1993–2001. In this paper, we report some comparative findings on the corrosion and surface chemical effects of the AP-CITROX procedure and the novel decontamination technology elaborated at our institution. On optimizing the operational parameters the latter technology may become suitable for the effective decontamination of both dismountable (e.g., MCP swivel) and separable (e.g., SGs) equipments. For this purpose experiments were performed. In this laboratory scale experiments, the passivity, morphology and chemical compositions of the treated surfaces of tube specimens were investigated by voltammetry, and SEM–EDX methods, respectively. The SEM–EDX results have revealed that the oxide removal is surprisingly uniform even after 2 or 3 consecutive cycles. The electrochemical studies have provided evidences that no unfavorable tendencies in the general corrosion state of the tube samples can be detected in the course of the chemical treatments.     

Pump Effect of a Capillary Discharge in Electrically Conductive Liquids

Among the configurations to generate plasma in electrically conductive liquids only the diaphragm and the capillary discharge schemes allow to generate plasma which is not in contact with one of the electrodes. Based on this concept, this work reports for the first time the development of an underwater plasma pump, in which the periodic electrical breakdown inside an asymmetrical (sub-)millimetre hole results in a net flow of aqueous solution through the hole without the use of any moving parts such as valves or diaphragms typically used in micropumps. Certain capillary geometries feature very stable flow rates and even allow altering flow direction by changing the power. By varying the hole’s dimensions, the range of time-independent flow rates covers more than one order of magnitude and as the discharge produces some of the strongest oxidants available, we believe that this concept might find application in fields as water decontamination and sterilization.     

Effect of the flow profile on separation efficiency in pressure‐assisted reversed‐polarity capillary zone electrophoresis of anions: Simulation and experimental evaluation

Capillary electrophoresis connected to electrospray ionization mass spectrometry is a promising combination to analyze complex biological samples. The use of sheathless electrospray ionization interfaces, such as a porous nanoelectrospray capillary emitter, requires the application of forward flow (either by pressure or electroosmosis) to maintain the electrospray process. The analysis of solute molecules with strong negative charges (e.g., aminopyrenetrisulfonate labeled glycans) necessitates a reversed‐polarity capillary electrophoresis separation mode, in which case the electroosmotic flow is counter current, thus pressure assistance is necessary. In this study, we compared the effect of forced convection with and without counter electroosmotic flow on the resulting separation efficiency in capillary electrophoresis based on flow profile simulations by computational fluid dynamics technique and by actual experiments. The efficiencies of the detected peaks were calculated from the resulting electropherograms and found approximately 950 000 plates/m for electrophoresis with counter electroosmotic flow, 20 000 plates/m with pressure only (such as would be in open tubular liquid chromatography), and 480 000 plates/m for electrophoresis with simultaneous counter electroosmotic flow and forward pressure assistance, which validates the simulation data.     

Decontamination of Chemical Warfare Agents by Novel Oximated Acrylate Copolymer

A novel acrylate copolymer, polymethylacrylate-β-(bromoacetyl ethyl)ester-co-N,N-dimethylacrylamide[P(MABE-co-DMAA)] was synthesized by the copolymerization of N,N-dimethylacrylamide and methylacrylate-β-(bromoacetyl ethyl)ester. Subsequently, the copolymer was oximated by 4-pyridinium aldoxime(4-PAM), and was abbreviated as PAM-P(MABE-co-DMAA). A maximum oxime conversion of 53.7% was obtained. The as-prepared oximated copolymer PAM-P(MABE-co-DMAA) effectively decontaminated chemical warfare agents(CWAs) including methylphosphonofluoridate(sarin or GB), S-2-(diisopropylamino)ethyl O-ethyl methylphosphonothioate (VX), and 2,2'-dichloroethyl sulfide(sulfur mustard, or HD). The detoxification rates were 90.6% for GB, 85.7% for VX, and 90.5% for HD. Chromogenic analysis, high performance liquid chromatography-mass spectrometry (HPLC/MS) and gas chromatography-mass spectrometry(GC/MS) were used to identify the decontamination products, and the decontamination mechanism was concluded to be a combination of nucleophilic substitution and a second order Beckmann rearrangement. Furthermore, the active decontamination materials, such as decontamination cloths and covers could be made from the oximated copolymer by virtue of its processability, as well as its strong ability to degrade CWA.     

Experimental investigation of the flow induced by artificial cilia

The fluid transport produced by rectangular shaped, magnetically actuated artificial cilia of 70 μm length and 20 μm width was determined by means of phase-locked Micro Particle Image Velocimetry (μPIV) measurements in a closed microfluidic chamber. The phase-averaged flow produced by the artificial cilia reached up to 130 μm s(-1) with an actuation cycle frequency of 10 Hz. Analysis of the measured flow data indicate that the present system is capable of achieving volume flow rates of V[combining dot above](cilia) = 14 ± 4 μl min(-1) in a micro channel of 0.5 × 5 mm(2) cross-sectional area when no back pressure is built up. This corresponds to an effective pressure gradient of 6 ± 1 Pa m(-1), which equals a pressure difference of 0.6 ± 0.1 mPa over a distance of 100 μm between two rows of cilia. These results were derived analytically from the measured velocity profile by treating the cilia as a thin boundary layer. While the cilia produce phase-averaged velocities of the order of O(10(2)μm s(-1)), time-resolved measurements showed that the flow field reverses two times during one actuation cycle inducing instantaneous velocities of up to approximately 2 mm s(-1). This shows that the flow field is dominated by fluid oscillations and flow rates are expected to increase if the beating motion of the cilia is further improved.     

Chemical analysis of bleach and hydroxide-based solutions after decontamination of the chemical warfare agent O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX)

Detailed chemical analysis of solutions used to decontaminate chemical warfare agents can be used to support verification and forensic attribution. Decontamination solutions are amongst the most difficult matrices for chemical analysis because of their corrosive and potentially emulsion-based nature. Consequently, there are relatively few publications that report their detailed chemical analysis. This paper describes the application of modern analytical techniques to the analysis of decontamination solutions following decontamination of the chemical warfare agent O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX). We confirm the formation of N,N-diisopropylformamide and N,N-diisopropylamine following decontamination of VX with hypochlorite-based solution, whereas they were not detected in extracts of hydroxide-based decontamination solutions by nuclear magnetic resonance (NMR) spectroscopy or gas chromatography-mass spectrometry. We report the electron ionisation and chemical ionisation mass spectroscopic details, retention indices, and NMR spectra of N,N-diisopropylformamide and N,N-diisopropylamine, as well as analytical methods suitable for their analysis and identification in solvent extracts and decontamination residues.     

A study of separation methods of 178m2Hf from irradiated ytterbium targets

The source material for the study of X-ray induced γ emission,^178m2Hf was obtained as Hf(OH)₄ by a variety of separation methods, such as precipitation, solvent extraction and ion exchange chromatography to isolate ^178m2Hf from an ytterbium target with a copper substrate, after irradiation in a cyclotron with α particles. The target was prepared by vacuum filtration technology. The overall chemical yield and decontamination factors of this separation process were measured with radioactive tracers. The results show that the chemical yield of the whole process is about 69 % for hafnium and the decontamination factor is very good for ⁶⁵Zn (~10⁵) and good for ¹⁷³Lu (~10³).     

Carrier-free separation of (115m)In from irradiated Cd by solvent extraction with 1-phenyl-3-methyl-4-caproylpyrazolone-5

A method is presented for the routine milking of the 41 2 -hr half-life nuclide (115m)In from its 2.3 day half-life parent (115m)Cd. The method utilizes the extraction of In and Cd from aqueous solution at various pH values, 1-phenyl-3-methyl-4-caproylpyrazolone-5 in isobutyl methyl ketone being used as extracting agent. A good decontamination factor was obtained and the yield of (115m)In from residual cadmium activity was 85-90%.     

Production of radiochemically and radionuclidically pure153Sm for medical applications

A procedure is described for the large scale production of radiochemically and radionuclidically pure¹⁵³Sm economically, from neutron irradiated natural Sm targets. Cation-exchange chromatography using 200–400 mesh Dowex-50×8 resin in the elution mode was used with 0.2M -hydroxyisobutyric acid (-HIBA) as the eluent at pH 4.7±1 and at 26±1 °C for this purpose. Typical decontaminations of carrier-free^(155+156)Eu radioactive impurities, of the order of 5×10², could be achieved in individual fractions, from millicurie amounts of¹⁵³Sm activity produced in milligram quantities of heavily neutron-irradiated natural Sm targets. Even though the¹⁵³Sm yields were at about 3% at these decontamination levels of impurities, the yields increased to an average of about 50% at about 95% level of decontamination of these impurities. It has been shown that the method is successful for producing radiochemically and radionuclidically pure¹⁵³Sm in sufficiently high radioactive concentrations for its probable conversion into¹⁵³SmEDTMP complex, a potential radiopharmaceutical useful in the palliative therapy of metastatic bone cancer.     

Dual function adsorbent-catalyst CuO-CeO2/NaX for temperature swing oxidation of benzene, toluene and xylene

A less common cyclic process of decontamination of benzene, toluene and o-xylene (BTX) using a dual function adsorbent-catalyst, referred to as the temperature swing oxidation, is introduced and discussed in this research. Preparation technique and characterization of the dual function adsorbent-catalyst CuO-CeO₂/NaX are presented. The temperature swing oxidation of BTX consists of two stages: adsorption of the VOC from the stream saturating the adsorbent-catalyst at different levels and catalytic oxidation of concentrated VOC induced by raising bed temperature at different flow rates of regenerative air. The results indicate that at lower saturation levels and lower flow rates of regenerative air a complete oxidation performance is better. The highest obtained values of the overall conversion of toluene, o-xylene and benzene into CO₂ and H₂O were 99.3, 99.8 and 77.5%, respectively, proving that the temperature swing oxidation using a dual function adsorbent-catalyst is a promising VOC decontamination technique under properly selected operating conditions.      

Recent R&D towards Aqueous Reprocessing of FBR Fuels

The mixed Pu-rich carbide spent fuel with a burn up of 155 GWd/t from the Fast Breeder Test Reactor is being reprocessed in a hot-cell facility by PUREX process. Based on the input from the operation of this facility, R&D activities were carried out to improve the recovery, decontamination factors, economy and to reduce the waste volumes. Reduction of uranyl ions in a continuous flow electrochemical reactor and electrolytic as well as chemical reduction of 4M HNO₃ from liquid waste could be accomplished in continuous mode. Using the optimized parameters, suitable electrolytic cells/experimental setups were designed for the plant capacity of 6 L/h. Studies on the extraction kinetics of Ru with 30% TBP in NPH revealed that better decontamination factor with respect to Ru can be achieved using fast contactors like centrifugal extractors (CEs). Towards developing a spent solvent recovery system to reduce organic waste volumes, a pilot plant was set up, which could recover diluent as top product of distillation column and 40% TBP as bottom product from inactive degraded solvent. A solvent recovery system using short path distillation was also developed for installation in hot cells.     

Was wissen Calamari über Sarin? Enzymatische Dekontamination von Nervenkampfstoffen

Together with detection and use of protective clothing, decontamination is the third important part in NBC defence and NBC protection. Enzymes play an important role in the research field of new and environmentally friendly decontaminants. In 1946, organophosphate cleaving enzymes were first mentioned, and in the next decades further enzymes (i.e., DFPase) against G‐type nerve agents were discovered. After the cloning of the DFPase gene sequence in the 90s, the potential of DFPase as an environmentally friendly decontaminant was shown. In technical decontamination experiments, it was shown that the conditions for an enzyme‐based decontamination concept could be met for one class of chemical agents. However, the success of a general enzyme decontamination concept depends on the discovery of new enzymes against other classes of chemical agents, i.e., mustard and VX.     

Self-generated hierarchically porous titania with high surface area: photocatalytic activity enhancement by macrochannel structure

Various hierarchical porous titania with high surface area over 600 m(2)/g have been synthesized via a spontaneous self-formation process from titanium alkoxides by a water adjusting approach using acetonitrile as reaction medium. The reactivity of metal alkoxides and the water content in acetonitrile medium on the resultant structure have been investigated. The porosities of the products were characterized by SEM, TEM and N(2) adsorption-desorption measurements. The observation on the evolution of porous structure with increasing water content in reaction system is essential for a better understanding of hierarchical porous structure formation over different length scales by this self-formation process. The creation of macro/micropores in photocatalytic titania materials has been found to enhance the photocatalytic activity due to both the action of macrochannels as light harvester and the easy diffusion effect of organic molecules. The present work shows clearly that hierarchically porous titania with the presence of macroporous structure and high surface area can be very efficient photocatalysts, suggesting their potential applications in water treatment as decontamination materials.     

Droplet formation in a microchannel network

A method is given for generating droplets in a microchannel network. With oil as the continuous phase and water as the dispersed phase, pico/nanoliter-sized water droplets can be generated in a continuous phase flow at a -junction. The channel for the dispersed phase is 100 microm wide and 100 microm deep, whereas the channel for the continuous phase is 500 microm wide and 100 microm deep. For given experimental parameters, regular-sized droplets are reproducibly formed at a uniform speed. The diameter of these droplets is controllable in the range from 100-380 microm as the flow velocity of the continuous phase is varied from 0.01 m s(-1) to 0.15 m s(-1).     

超支化聚合物化学键合毛细管电泳柱的制备及其对蛋白质的分离行为

分别合成了以三羟甲基丙烷和季戊四醇为核的超支化聚(胺-酯),并对其进行了红外测定、羟值测定、粘度测定等表征。采用化学键合方法将其涂于毛细管内壁,并测定涂层柱的电渗流以及对碱性蛋白质的分离能力,结果表明,涂层柱能有效地抑制碱性蛋白质在毛细管内壁上的吸附,大大降低电渗流;以三羟甲基丙烷为核的超支化聚(胺-酯)涂层柱的塔板数达105/m,而以季戊四醇为核的超支化聚(胺-酯)涂层柱的分离柱效更高,塔板数达107/m。实验结果表明这两类涂层柱都具有较好的分离效果和稳定性。     

Covalent Organic Frameworks(COFs) for Sequestration of99TcO4–

Covalent organic frameworks(COFs), as a class of crystalline porous materials with periodic lattices and porous structures, have received extensive attention in the fields of gas storage and separation, energy storage, catalysis and optoelectronics and so on. However, COFs are still in their infancy in the field of nuclear waste treatment, especially for sequestration of long-live problematic radionuclides, such as ⁹⁹Tc. Battle of decontamination of pertechnetate(TcO₄^–), a main existence of ⁹⁹Tc under aerobic environments, is far from finished. In this review, recent progresses of COFs and some relative materials in the sequestration of pertechnetate, and perspective on surmounting the unmet issues are elucidated.