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.     

Hydrodynamics of the effectiveness of the AP-CITROX decontamination technology

During the optimization of the AP-CITROX decontamination technology the effect of the different flow rates of the decontamination solutions on the radioactive contamination and corrosion state of stainless steel tube samples originating from steam generators of Paks NPP were studied by a pilot-plant circulation system. The results have proved that a significant increase (up to 2.89 m/s) in the flow rate of the decontamination solution in the 1-5 steps is highly recommended and in order to improve the passivity of the surfaces it should be kept as low as possible (0.5 m/s) during the passivation.     

Recovery of technetium adsorbed on charcoal</p> </p>

Two methods capable of near complete recovery of technetium adsorbed on charcoal are presented. The first involves liquid extraction of the technetium from the charcoal by hot 4M nitric acid. An average recovery of 98% (n=3) is obtained after three rounds of extraction. The second method involves dry ashing with air in a quartz combustion tube at 400-450 °C. This method yields an average recovery of 96% (n=5). Other thermal methods were attempted, but resulted in reduced recovery and incomplete material balance.</p> </p>     

Radiation effects on gaseous iodine at very low concentrations</p> </p>

Summary Exploratory experiments have been carried out to investigate the effects of gamma-radiation on iodine aerosols under various chemical conditions. The results indicate that iodide ions (I^-) in aerosol can be readily oxidized to I₂ and HIO, and some iodide ions may be converted to organic iodine when organic additives are present in the KI solution from which the aerosol is generated. The results also suggest that the chemical transformation of irradiated iodine aerosol depends on the chemical environment both carrier gas and iodide solution.</p> </p>     

Cation-exchange separation of uranium from thorium in nitric acid medium</p> </p>

Summary Sorption behavior of Th and U on cation-exchange resins was investigated from nitric acid medium by both batch and column methods. The cation-exchange studies involved the sorption of UO₂²⁺ and Th⁴⁺ and their cationic complexes onto Dowex 50Wx8 and Dowex 50Wx4 resins (50-100 mesh). The batch data yielded a separation factor (K_d,Th/K_d,U) value of >100 for the cation-exchanger, Dowex 50Wx4 at 1-2M HNO₃. Separation of uranium from thorium was also carried out by column method in nitric acid medium using cation-exchangers, Dowex 50Wx4 as well as Dowex 50Wx8. While uranium elution was possible at 1M HNO₃, Th could be eluted only at higher concentration of nitric acid (>6M). The stripped solution emanating from a mixer settler employing di-2-ethyl hexyl isobutyramide as extractant and feed solution similar to THOREX process comprising 350 mg/l U and 380 mg/l Th in 0.75M HNO₃ was loaded on the column and the decontamination factor value for U in the product was >1000.</p> </p>     

Simultaneous measurement of gamma-rays and neutron fluences</p> using a HPGE detector</o:p></p> </p>

Summary A simultaneous determination of gamma and neutron fluences in a mixed neutron + gamma field can be achieved by gamma-ray spectrometry, optimizing the moderator-converter-detector assembly and measuring both the direct gamma-lines and the neutron induced prompt gammas. For the prompt gamma-lines a combination of high efficiency and low background is the goal, and it can be best achieved if the gamma-energy is in the range above about 1 MeV up to 2.5 MeV. The optimal moderator-converter thickness can be determined experimentally. Most converter elements produce gamma-rays in the low energy range. If chlorine is used as a converter, the 1164.7 keV peak and the 1950-1960 keV peaks seems to be a good choice. A very practical material containing chlorine is PVC. It is an efficient moderator, it is solid, common, and can be handled easily.</p> </p>     

New data for the characterization of Milos obsidians</p> </p>

Summary Newly produced fission track (FT), instrumental neutron activation analysis (INAA) and micro-Raman spectrometry data have been used to characterize the classical source areas of the Milos obsidians better and to check the provenance of obsidian artefacts. The Bombarda-Adhamas and Demenegaki obsidians yielded indistinguishable FT ages 1.57±0.12 and 1.60±0.06 My, respectively, in agreement with previous FT data. By INAA analyses it was possible to discriminate between the three obsidian sources on Milos: Bombarda-Adhamas, Demenegaki and A. Ioannes. Raman spectroscopy has been found to be a valuable technique to gain a chemico-structural characterization of a given obsidian population in terms of dissolved water content and microlite distribution/composition.</p> </p>     

Cs and Sr removal from solution using potassium nickel hexacyanoferrate impregnated zeolites</p> </p>

Summary Potassium nickel hexacyanoferrate, KNiFC, was incorporated in the porous matrix of zeolites by successive impregnation with Ni(NO₃)₂ and</o:p></p> K₄Fe (CN)₆.¹ CFC and PFC exchangers were first prepared by impregnating the potassium nickel hexacyanoferrate into the clinoptilolite and the synthetic P zeolite, respectively. Ion-exchange isotherms and breakthrough curves were plotted. Results showed that the CFC sorbent is suitable for removal of Cs⁺ where PFC is more suitable for Sr²⁺. Negative effect of Na⁺ as a competing ion in these exchangers was less than in the parent zeolites. Isotherm plots fitted the Langmuir equation.</p> </p>     

Removal of uranyl ions from wastewaters using cellulose and modified cellulose materials</p> </p>

Summary Three silylcellulosic derivatives with different substitution degree were examined as sorbents for uranyl ions. The adsorption rate and capacity of cellulose and modified cellulose were investigated in aqueous media, at various pH and temperature values. The polymer - metal complexes of UO₂²⁺ were characterized by infrared and electronic spectra, and thermogravimetry. The thermal behavior of cellulose (C), trimethylsilyl - cellulose (tmsc, SD= 2.85) and triphenylsilyl - cellulose (TPSC1, SD=2.89 and TPSC2, SD =2.70) and their complexes with uranyl ions in atmospheric air has been studied between room temperature and 600 °C. The Coats-Redfern method was applied to estimate the kinetic parameters. The results revealed that the complexation of C and TMSC with UO₂²⁺ increases the thermal stability.</p> </p>     

Preconcentration of 198Au in a green alga, Rhizoclonium</p> </p>

Summary The bioaccumulation of ¹⁹⁸Au radionuclide, by Rhizoclonium riparium a member of Chlorophyceae has been studied. It has been observed that accumulation of gold on Rhizoclonium is almost pH independent and slightly higher at basic pH. Accumulation of gold was studied with ¹⁹⁸Au radiotracer, 0.1, 1 and 5 ppm concentrations of gold. It has been concluded from the biochemical analysis that the gold accumulation is due to adsorption in the cellulose and not in protein, fat and carbohydrate. Accumulated gold was recovered when washed with conc. HNO₃.</p> </p>     

Cascade ultrafiltering of 210Pb and 210Po in freshwater using a tangential flow filtering system</p> </p>

Summary A rapid method was developed using ultrafilters with a tangential flow filtering system for molecular size separation of naturally occurring ²¹⁰Pb and ²¹⁰Po in a freshwater sample. Generally, ultrafiltering of a large volume water sample for measuring the nuclides was too time consuming and not practical. The tangential flow filtering system made the filtering time short enough to adapt for in-situ ultrafiltering the large volume sample. In this method, a 20 liter water sample was at first passed through the 0.45mm pore size membrane filter immediately after sample collection to obtain suspended particle matter [>0.45mm particulate fraction (PRT)]. Two ultrafilters (Millipore Pellicon 2^ò) were used sequentially. The nuclides in the filtrate were separated into three fractions: high molecular mass (100 kDa-0.45mm; HMM), low molecular mass (10 k-100 kDa; LMM) and ionic (<10 kDa; INC) fractions. It took 80 minutes to process the sample after collection. The cut-off molecular size of each ultrafilter was confirmed by size exclusion chromatographs (SEC) of the LMN and the HMM fractions. Adsorption of the nuclides and organic compounds in the sample onto the ultrafilters was negligibly small. Good reproducibility of the nuclide concentrations in each fraction was confirmed by repeated experiments. The method was successfully applied to obtaine the molecular size distributions of ²¹⁰Pb and ²¹⁰Po in an oligotrophic lake, Lake Towada located in the northern area of Japan.</p> </p>     

Macro micro separation of selenium and tellurium: Application to NAA</p> </p>

Summary A simple pre-irradiation separation approach has been worked out for the determination of traces of tellurium in high purity selenium followed by neutron activation analysis (NAA) for the end determination of the analyte/s. The difference in volatilities of these elements has been utilized for the separation of the analyte from the matrix. The complete volatility of selenium at ~600 °C was established using neutron activation analysis and selenium radiotracer. Standard addition was used to validate the results. The proposed method of separation of selenium prior to irradiation could make the determination of tellurium possible and also improved the detection limit by several folds.</p> </p>     

Sorption of Co, Cs, Sr and I onto argillaceous rock as studied by radiotracers</p> </p>

Summary Sorption of⁶⁰Co,⁸⁵Sr, 137Cs and¹²⁵I have been studied on samples originated from Boda (siltstone-) claystone formation (BCF) (Hungary). The distribution of K_dvalues have been determined in static batch experiments using natural groundwater. The order of sorption of isotopes was Co>Cs>Sr>I, where iodine exhibits sorption properties in a modest extent. The sorption isotherm was determined for Cs from measurements carried out in 10^-5-10^-1M initial concentration range. The isotherm can be described with non-linear Freundlich approximation in the range of</o:p></p> 10^-7-10^-4M equilibrium concentration. At concentrations >10^-2M the isotherm achieves saturation. Hence, it is suggested that sorption of Cs on BCF is dominated by cation-exchange reactions on the illite mineral component. In the case of Co and Sr, precipitation reactions occurred during the experiments performed with carrier-containing solutions. This can be attributed to the low values of solubility product constants of SrCO₃, SrSO₄and Co(OH)₂, formed from anions present in the natural groundwater.</p> </p>     

Removal of radium from sand filters by inorganic acids</p> </p>

Summary Sand filters are used in water treatment stations to remove particulate matter from underground water, where iron and manganese are collected forming thin oxide films. These oxides of iron and manganese adsorb radium from underground water. Radium concentration increases in time on the filters, and consequently the level of radioactivity increases in the station. The removal of adsorbed radium on sand using inorganic acids was studied. Good efficiency of radium removal was obtained by controlling different parameters like temperature, time, pH, addition of competitive cations and anions. It was found that hydrochloric acid is the best for radium removal from sand filters. Maximum removal obtained was about 60% at 5M BaCl₂ and 2M HCl at 50 °C for 180-minute contact time. Kinetic parameters of the removal process were studied and compared with literature data.</p> </p>     

Liquid-liquid extraction of 233Pa(V) with Aliquat 336</p> </p>

Summary The extraction of protactinium with Aliquat 336 (methyl-tri-caprylyl ammonium chloride) in toluene, cyclohexane and chloroform from HCl, HNO₃, H₂SO₄, HClO₄, HF and mixed HCl-HF media was investigated by radioactive tracer technique. Distribution ratios of protactinium between the aqueous solution and the organic phase were determined as a function of shaking time, concentrations of acid in aqueous solution phase, extractant concentration and type of diluents in the organic phase. Aliquat 336 can almost quantitatively extract protactinium from strong HCl solution. At the same time, small amounts of HF in HCl solutions have a strong effect on Pa distribution.</p> </p>     

Sorption of Co(II) ong-alumina in the presence and absence of fulvic acid</p> </p>

Summary The removal of heavy metal ion Co(II) from aqueous solution was studied usingg-Al₂O₃ by batch technique. The experiments were performed at T=20±2 °C, in 0.01M NaNO₃ solutions and under aerobic conditions. The effect of pH, ionic strength, fulvic acid (FA) and alumina amount on the sorption of Co(II) on alumina were also investigated. The pH affected the sorption of Co(II) significantly as compared with the effect of FA and ionic strength. The results indicated that strong chemical bonds are formed between Co(II) and functional groups of the bare or FA coated alumina, and a precipitation of Co(II) takes place on the alumina surface, induced by a transition from the adsorption to surface. The addition sequences of Co/FA on Co(II) sorption were also studied: the sorption of Co(II) in the ternary system was found independent of addition sequences.</p> </p>     

Seasonal variations of atmospheric210Pb and7Be concentrations at Kumamoto, Japan and their removal from the atmosphere as wet and dry depositions</p> </p>

Summary A relatively simple chemical separation procedure has been developed for the simultaneous determination of⁸⁹Sr and ⁹ 0Sractivities in water samples and on aerosol-filters of the Nuclear Power Plant (NPP) Paks origin. The procedure combines the cation-exchange chromatographic (Dowex 50 WX 8 resin) and solid phase extraction (EIChroM Sr.Spec?, DC18C6 crown ether) steps. The beta-radiation of radionuclides can be measured directly after the chemical separation by LSC. The activities of⁸⁹Sr,⁹⁰Sr and⁹⁰Y are calculated from an over determined set of equations using a method of constrained optimization technique. The equations are based on LSC measurements performed in three counting windows plus the⁹⁰Sr-⁹⁰Y decay law. The chemical yield of strontium is determined by ICP-AES. The lowest limits of detectable activity, for the measurement time of 600 minutes, are 30 mBq/sample and 18 mBq/sample for⁸⁹Sr and⁹⁰Sr, respectively.     

Mössbauer study of Fe/S and Fe/O films produced by laser ablation of pyrite and hematite</p> </p>

Summary Pyrite FeS₂ was laser-deposited onto Al substrates at various temperatures, and the M?ssbauer spectra of the films were measured. The yields and the M?ssbauer parameters of FeS₂ and FeS changed depending on the formation temperature, because of the sulfur deficiency in the lattice structures. In addition, hematite Fe₂O₃ was employed as a laser-ablation target, and FeO and Fe₂O₃ were deposited on SiO₂/Si substrates. It was shown that laser-deposition of compounds can produce films that have different chemical species than the laser-evaporated materials.</p> </p>     

Radiological hazard and radiogenic heat production in some building materials in upper Egypt</p> </p>

Summary Samples of limestone, sand, marble, clay brick, red brick, gypsum, Portland cement and white cement collected from upper Egypt used in building manufacturing have been analyzed for the natural radionuclides ²²⁶Ra, ²³²Th and ⁴⁰K usingg-ray spectrometry. The specific concentrations for ²²⁶Ra, ²³²Th and ⁴⁰K, ranged from 20-88, 13-115 and 54-304 Bq/kg, respectively. The average specific activities of these radionuclides were compared. Higher values of ²²⁶Ra and ²³²Th could be noticed in marble while that of ⁴⁰K was in red bricks. Radium equivalent activities, dose rate and the annual gonadal dose equivalents AGDE were calculated for the measured samples to assess the radiation hazard arising from using those materials in the construction of dwellings. The radioactive heat production values of the selected materials have also been determined. They vary from a minimum of 0.41 for white cement to a maximum of 5.52mW/m³ for marble samples. The calculated heat-production values are quite similar to those estimated in Corsica.</p> </p>     

Inorganic ion-exchangers in radioactive waste management</p> </p>

Summary The uptake of indigenously synthesized amorphous stannic and zirconium phosphate was assessed for, one of the important fission fragment, cesium from aqueous solutions using a radiotracer technique. A virtual increase in sorptive concentration (from 1.0 ^. 10^-8 to 1.0 ^. 10^-2 mol ^. dm^-3) and pH (from 2.4 to 10.2) and temperature (from 303 to 333 K) enhanced the uptake of cesium on stannic phosphate. However, the extremely high degree of uptake of cesium on zirconium phosphate was almost unaffected with the dilution beyond 10^-5 mol ^. dm^-3 and pH (i.e., from 2.4 to 10.2) and temperature (from 303 to 323 K). Irreversible uptake occurring for these solids follow the Freundlich adsorption isotherm and the presence of several complexing agents viz., sulphate, phosphate, glycine and EDTA did not affect appreciably the uptake of cesium on zirconium phosphate but it did affect for stannic phosphate system. Both these solids showed good radiation stability towards a 11.1 GBq Ra-Be neutron source having neutron flux ca. 3.2 ^. 10⁶ n ^. cm^{-2 .} s^-1 and associated with a nominalg-dose of ca. 1.72 Gy/h, at least for the uptake of cesium.</p> </p>