Complementary spectroscopic techniques to model the association of contaminant uranium with structural surfaces

Contaminant uranium poses unique problems for decontamination of former weapons processing and nuclear power facilities, as well as chemical plants, waste storage sites and former mining facilities. In addition, dealing with the possibility of intentional (i.e., a terrorist act) or accidental release of radioactive material in a populated area requires an accurate understanding of the nature of the association of such material with structural surfaces. These surfaces must also be considered in the context of repeated contamination, and the importance of atmospheric exposure, interaction with other possible contaminants, and corrosion or surface degradation due to such exposure must be taken into account. Complementary spectroscopic techniques, especially surface spectroscopies, are essential in developing models for the interaction of contaminants with surfaces and interfaces. In this review (which also presents new data on uranium association with corroding steel surfaces), we collect models of this association as determined by spectroscopic techniques, assess the important considerations in the development of more accurate models, and address some of the questions which remain.     

Chemical, sensory and microbiological changes of gamma irradiated coconut cream powder

A study was carried out to determine optimum decontamination dose for a locally manufactured coconut cream powder. Samples were gamma irradiated (0–15 kGy) and ageing process was achieved using GEER oven at 60 °C for 7 days, which is equivalent to one-year storage at room temperature. Iodine value (IV), ranging from 4.8 to 6.4, was not affected by radiation doses and storage, however peroxide value and thiobarbituric acid (TBA) generally increased with radiation doses. In most samples, peroxide value (meq/kg) reduced after storage, whilst the TBA (mg malonaldehyde/kg), indicator for product quality, slightly increased. The sensory evaluation conducted using 25 taste panellists indicated that scores on odour, creamy taste and overall acceptance for all irradiated samples at more than 5 kGy were significantly lower (P<0.05) than the control. However, the panellists could not detect any significant differences among the irradiation doses (P>0.05). All stored products were significantly different in colour, creamy taste, odour and overall acceptance (P<0.05) when compared to the non-stored non-irradiated control. Microbiological count of the samples prior to irradiation was in the range of 1×10²–1.7×10³ cfu/g with no detection of Salmonella sp. and Escherichia coli. No microbial colonies were detected after irradiation. Based on the TBA and overall sensory acceptance, gamma irradiation of 5 kGy was found to be the optimum dose and lower doses can be considered to decontaminate coconut cream powder.     

Decontamination of pesticide packing using ionizing radiation

The Brazilian agriculture activities have consumed about 288,000 tons of pesticides per year conditioned in about 107,000,000 packing with weight of approximately 23,000 tons. The discharge of empty plastic packing of pesticides can be an environmental concern causing problems to human health, animals, and plants if done without inspection and monitoring. The objective of this work is to study the ionizing radiation effect in the main pesticides used in Brazil for plastic packing decontamination. Among the commercial pesticides, chlorpyrifos has significant importance because of its wide distribution and extensive use and persistence. The radiation-induced degradation of chlorpyrifos in liquid samples and in polyethylene pack was studied by gamma radiolysis. Packing of high-density polyethylene (HDPE) three layer coextruded, named COEX, contaminated with chlorpyrifos, were irradiated using both a multipurpose Co-60 gamma irradiator and a gamma source with 5000 Ci total activity Gamma cell type. The chemical analysis of the chlorpyrifos was made using a gas chromatography associated to the Mass Spectrometry—GCMS from Shimadzu Model QP 5000. Gamma radiation was efficient for removing chlorpyrifos from the plastic packing, in all studied cases.     

Characteristic X-ray detector: In-situ imaging of radioactive contaminant distributions

The characteristic X-ray detector (CXRD), a CsI(Tl) scintillator with a 50-mm diameter, is a directional X-ray sensor that measures characteristic X-rays from radioactive material, such as ¹³⁷Cs, and identifies the direction of radioactive contamination. We evaluated a CXRD and visualized the distribution of radioactivity in the contaminated area near the Fukushima Dai-ichi nuclear power station, where the ambient dose equivalent rate was 2.1 μSv/h at 1 m above ground level. We found a good correlation between the characteristic X-ray fluxes and the distribution of radioactive contaminants with a 0.823 Pearson product–moment correlation coefficient.     

CO2 laser assisted removal of UO2 and ThO2 particulates from metal surface

Pulsed laser assisted removal of uranium dioxide and thorium dioxide particulates from stainless steel surface have been studied using a TEA CO₂ laser. Decontamination efficiency is measured as a function of laser fluence and number of pulses. Threshold fluence for the removal of UO₂ particulates has been found to be lower than that required for the removal ThO₂ particulates. Usage of a ZnSe substrate, that is transparent to the laser wavelength used here, enabled us to decouple the cleaning effect arising out of absorption in the particulates from that in the substrate and has contributed towards understanding the mechanism responsible for cleaning. The experimental observations are also corroborated by simple theoretical calculations.     

Removal of uranium (VI) from nuclear effluents onto aluminophosphate and silicoaluminophosphate molecular sieves

Aluminophosphate and silicoaluminophosphate molecular sieves with both five (AFI) and eleven (AEL) type structures are synthesized by hydrothermal crystallization at 473 K, using tripropylamine and dipropylamine as a structure-directing template. The as-prepared AFI and AEL sieves are characterized and then assessed as sorbents for uranium (VI) from radioactive effluents. The sorption process is used to reduce the volumes of effluents and convert them into a stable solid waste. The batch experimental studies are carried out to evaluate the AEL and AFI structure effect on the removal of uranium. The AlPO₄-5, SAPO-5, AlPO₄-11 and SAPO-11 are applied to radioactive effluents with different activities obtained from Nuclear Research Center of Draria, Algeria. Important decontamination factor values are obtained for AFI sorbents. Thermodynamic parameters, namely, the enthalpy (ΔH), entropy (ΔS) and free energy (ΔG) for each sorption process are calculated. The collected results indicated that sorbents are effective materials for the removal of uranium (VI) ions, the sorbent with AFI structure being a highly effective material for the removal of uranium (VI) ions from nuclear effluents.     

Decontamination of chemical warfare agents using perchloroethylene–Marlowet IHF–H2O-based microemulsions: wetting and extraction properties on realistic surfaces

At the present time, considerable efforts are being made to develop new media for the decontamination of a variety of toxic compounds. In the present contribution, new microemulsions with promising properties are presented. Moreover, the decontamination of surfaces, with an emphasis on varnished metal surfaces of exterior and interior equipment, is investigated using these microemulsions. Studies of the phase behavior of the system water–perchloroethylene–IHF–2-propanol are reported and the microemulsion phases are recognized. The wetting behavior on contaminated surfaces and the extraction capabilities with respect to contaminants are essential for an efficient decontamination. Hence, suitable microemulsions are identified on the basis of these properties. The decontamination efficiency of these microemulsions is first estimated on the basis of the ability to wet typical chemical nonresistant varnished steel sheets, which are authentic model systems for real surfaces. Afterwards, promising microemulsions and, as reference, different solvents are tested with respect to their capability to solubilize sulfur-mustard agent, again using realistic surfaces contaminated with this chemical warfare agent. Several microemulsions are found, which have the desired properties.     

Microbiological decontamination of natural honey by irradiation

Degree of microbiological decontamination, organoleptic and physico-chemical properties of natural honeys were investigated after radiation treatment. Seven kinds of honeys were irradiated with the beams of 10 MeV electrons from a 10 kW linear accelerator “Elektronika 10-10” at the dose 10 kGy.

It was shown, that after irradiation, the total count of aerobic and anaerobic bacteria and moulds decrease by 99%. The antibiotic value in investigated honeys increased in turn from 1.67 to 2.67 after irradiation. Such factors and parameters of investigated honeys as their consistency, content of water and saccharose, acidity, the diastase and 5-HMF values were not changed significantly after irradiation.

Decontamination by irradiation is a process which allows us to obtain high microbiological purity of honeys. It is especially needed, when honeys are used in surgical treatment of injuries and in nutrition of babies with food deficiency.     

The pharmacological activity of medical herbs after microbiological decontamination by irradiation

In the Institute of Nuclear Chemistry and Technology research on microbiological decontamination of medicinal herbs by irradiation has been carried out since 1996. It was shown that using ionizing radiation (a dose of 10 kGy) can obtain satisfactory results of microbiological decontamination of these products. The content of essential biologically active substances such as essential oils, flavonoids, glycosides, anthocyans, antra-compounds, poliphenoloacids, triterpene saponins, oleanosides and plants mucus did not change significantly after irradiation. Pharmacological activity of medicinal herbs has been found satisfactory after microbiological decontamination by irradiation.     

Research and application of inorganic selective sorbents at Mayak PA

This work has been performed in order to identify selective inorganic sorbents for caesium and strontium. Thin-layer sorbents with nickel ferrocyanide embedded in an inert matrix were found to be the best for caesium. Sorbents including non-stoichiometric manganese dioxide were selected for strontium. Bench tests have been carried out on the purification of desalted water of SNF storage-pool from ¹³⁷Cs, and on the purification of contaminated natural water from ⁹⁰Sr. The facility for synthesizing the ferrocyanide sorbent with the registered mark ‘Seleks-CFN’ has been brought into operation. The sorbent ISM-S seems promising for ⁹⁰Sr decontamination. To cite this article: M.V. Logunov et al., C. R. Chimie 7 (2004).

Résumé

Recherches et applications sur l’utilisation de sorbants spécifiques à Mayak. Des sorbants sélectifs du césium et du strontium ont été identifiés. Pour le césium, le meilleur s’avère être le ferrocyanure de nickel, s’il est utilisé sous forme de couche mince. Pour le strontium, on a sélectionné des composés non stœchiométriques de dioxyde de manganèse. On a mené des tests visant à épurer en césium l’eau des piscines d’entreposage des combustibles nucléaires usagés, et en strontium des eaux contaminées. Une installation industrielle permettant de préparer le sorbant à base de ferrocyanure de marque « Seleks-CFN » a été réalisée. Le sorbant ISM-S semble prometteur pour la décontamination en strontium. Pour citer cet article : M.V. Logunov et al., C. R. Chimie 7 (2004).