Volume 98, Issue 5 -

Interactions of the acidothermophilic archaeon Sulfolobus acidocaldarius DSM 639 with U(VI) were studied by using a combination of batch experiments, X-ray absorption spectroscopy (XAS), and time-resolved laser-induced fluorescence spectroscopy (TRLFS). We demonstrated that at pH 2 this archaeal strain possesses a low tolerance to U(VI) and that its growth is limited to a uranium concentration below 1.1 mM. At similarly high acidic conditions (pH 1.5 and 3.0), covering the physiological pH growth optimum of S. acidocaldarius , at which U(VI) is soluble and highly toxic, rapid accumulation of the radionuclide by the cells of the strain occurred. About half of the uranium binding capacity was reached by the strain after an incubation of five minutes and nearly total saturation of the binding sites was achieved after 30 min. Both, EXAFS- and TRLF-spectroscopic analyses showed that the accumulated U(VI) was complexed mainly through organic phosphate groups. The EXAFS measurements revealed that U(VI) is coordinated to the organic phosphate ligands of the archaeal cells in a monodentate binding mode with an average U–P bond distance of 3.60±0.02 Å.

Hollow fibre supported liquid membrane (HFSLM) studies were carried out for the selective recovery of uranium from THOREX feed solution (0.2 g/L U+200 g/L Th+0.03 M HF+0.1 M Al(NO 3 ) 3 at 4 M HNO 3 ) using di(2-ethylhexyl) isobutyramide (D2EHIBA) as the carrier and distilled water as the strippant. About 85% of uranium was selectively transported into the receiver phase in 30 min with <1% contamination from thorium. On the other hand, under identical conditions of feed and strip solutions, about 90% of uranium was recovered in the same time when 5% TBP (tri- n -butyl phosphate) was used as the carrier, but a relatively large amount of thorium (>10%) was also co-transported to the product side. Strip phase acidity analysis revealed significant amount of acid co-transport with both the carriers. Acid transport was found to increase with the total salt content of the feed solution. The transport of metal ions was explained with the help of a theoretical model. Stability of the liquid membrane was also studied over about 5 d for long term reusability.

During a hypothetical nuclear power plant accident, fission products may be released from the fuel matrix and then reach the containment building and the environment. Ruthenium is a very hazardous fission product that can be highly and rapidly released in some accident scenarios. The impact of the atmosphere redox properties, temperature, and fuel burn-up on the ruthenium release is discussed. In order to improve the evaluation of the radiological impact by accident codes, a model of the ruthenium release from fuel is proposed using thermodynamic equilibrium calculations. In addition, a model of fuel oxidation under air is described. Finally, these models have been integrated in the ASTEC accident code and validation calculations have been performed on several experimental tests.

This paper presents the results on the use of short columns (3−5 cm long) with small particle size (1.8 μm) for high performance liquid chromatographic separation of individual lanthanides and uranium from plutonium as well as uranium from thorium to achieve rapid separations i.e. separation time as short as 3.6 min for individual lanthanides, 1 min for thorium-uranium and 4.2 min for uranium from plutonium. These advantages can be exploited to significantly reduce analysis time, liquid waste generation as well as dose to operator when radioactive samples are analysed e.g. burn-up determination. In the present work, a dynamic ion-exchange chromatographic separation technique was employed using camphor-10-sulfonic acid (CSA) as the ion-pairing reagent and α-hydroxy isobutyric acid (α-HIBA) as the complexing reagent for the isolation of individual lanthanides as well as the separation of uranium from thorium. Uranium was separated from Pu(III) as well as Pu(IV) by reverse phase HPLC technique. The reverse phase HPLC was also investigated for the isolation and quantitative determination of uranium from thorium as well as lanthanide group from uranium. The dynamic ion-exchange technique using small particle support was demonstrated for measuring the concentrations of lanthanide fission products such as La, Ce, Pr, Nd and Sm in the dissolver solution of fast reactor fuel. Similarly, the assay of uranium in the dissolver solution of fast reactor was carried out using reverse phase HPLC technique. The rapid separation technique using reverse phase HPLC was also demonstrated for separation of lanthanides as a group from uranium matrix; samples of LiCl-KCl eutectic salt containing chlorides of lanthanides in uranium matrix (typically 1:2000) were analysed.

Gamma spectrometric determination of thorium in sintered thoria dissolved in strong phosphoric acid was studied using a high purity germanium (HPGe) detector. 232 Th was determined using the highly abundant (27%) gamma ray (911.4 keV) emitted by its daughter 228 Ac. The count rates in peak regions were plotted against the amount of thorium present in thorium nitrate working standard solution to obtain a calibration curve and the extent of thoria dissolved in 88% phosphoric acid was determined. Further studies on determination of thorium were carried out using thorium phosphate solutions, instead of using thorium nitrate working standard solutions. The solution of thorium phosphate obtained after quantitative dissolution of thoria in 88% phosphoric acid was also found to give a linear calibration curve at 911.4 keV. Using the calibration curves, expected count rates for thorium in sintered thoria dissolved in 88% phosphoric acid were calculated and were in good agreement (±3%) with the observed count rates.

The effects of pH, ionic strength, temperature, humic acid (HA) and fulvic acid (FA) on the sorption of radionuclide 63 Ni(II) to MnO 2 have been investigated by using batch techniques. The results indicated that the sorption of 63 Ni(II) on MnO 2 is obviously dependent on pH values but independent of ionic strength. The presence of HA/FA strongly enhances the sorption of 63 Ni(II) on MnO 2 at low pH values, whereas reduces 63 Ni(II) sorption at high pH values. The sorption of 63 Ni(II) on MnO 2 is attributed to inner-sphere surface complexation rather than outer-sphere surface complexation or ion exchange. The diffuse layer model (DLM) is used to simulate the experimental data well with the aid of FITEQL 3.2. The thermodynamic parameters (Δ H 0 , Δ S 0 , Δ G 0 ) are also calculated from the temperature dependent sorption isotherms, and the results suggest that the sorption of 63 Ni(II) on MnO 2 is a spontaneous and endothermic process.

China has planned to deal with the high-level radioactive wastes (HLW) in the middle of this century with deep geologic disposal method. The release of heat from HLW may cause the rise of temperatures in the surrounding backfilling materials or even the host rock of a repository. This brings about the concerns that the temperature elevation in the host rock may change the diffusion characteristics of key radionuclides and have some unpredictable effects in the performance assessment. In this paper, the influence of temperature on the diffusion of 125 I − in Beishan Granite is studied by through diffusion method. The effective diffusion coefficients ( D e ) of 125 I − in the granite from 27 to 50 °C are obtained and analyzed as a function of temperature. Our result indicated that the relationship between D e and temperature can be described by the modified Nernst equation, and the formation factors ( F f ) of the granite from 27 to 50 °C is constant with an average value of 1.03×10 −4 .

Degradation of priority organic pollutant methoxychlor in methanol solution by gamma irradiation under varied experimental conditions has been optimized. The solution of methoxychlor was air saturated before irradiation. The extent of radiolytic degradation efficiency was monitored by reversed phase HPLC-UV; two major and two minor degradation products were detected. For 5 kGy gamma radiation dose at a rate of 200 kGy h −1 ≥95% methoxychlor was degraded. The degradation was also monitored by GC-ECD and the degradation products were identified using GC-MS after comparing their mass spectra with the NIST 98 m mass spectral library. It is proposed that major degradation occurs through dechlorination, dehydrochlorination, by the detachment of methoxyphenyl from methoxychlor and by interaction of other radicals generated by the methanol radiolysis. The probable reaction schemes for the formation of products have been proposed. Most of the generated products were methoxy substituted, probably due to the availability of the methoxy radical from methanol radiolysis. The identified radiolytic products of methoxychlor and the removal efficiency have been compared with those of UV photolysis. It is observed that although the source of degradation is somewhat different, the end products or radical generated species are of similar nature.