Sorption and desorption of Co(II) on montmorillonite in presence and absence of fulvic acid

Sorption and desorption of Co(II) on montmorillonite under ambient conditions as a function of pH, ionic strength and fulvic acid are studied by batch technique. The results indicate that the sorption of Co(II) is dependent on pH, and ionic strength. The sorption-desorption hysteresis is found in the desorption tests. Surface complexation is considered as the main sorption mechanism of Co(II) on montmorillonite. The presence of fulvic acid (FA) enhances the sorption of Co(II) on montmorillonite. Montmorillonite is considered as a promising candidate for the solidification and pre-concentration of Co(II) from large volume of solutions.     

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>     

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>     

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>     

Sorption behavior of Co(II) on γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> in the presence of humic acid

The fate and transport of toxic metal ions and radionuclides in the environment is generally controlled by sorption reactions. The extent of sorption of divalent metal cations is controlled by a number of factors including cosorbing or complexing. In this work, the effects of pH, humic acid HA/Co(II) addition orders, ionic strength, concentration of HA, and foreign cations on the Co(II) sorption on γ-Al₂O₃ in the presence of HA were investigated. The sorption isotherms of Co(II) on γ-Al₂O₃ in the absence and presence HA were also studied and described by using S-type sorption model. The experimental results showed that the Co(II) sorption is strongly dependent on the pH values, concentration of HA, but independent of HA/Co(II) addition orders, ionic strength, and foreign cations in the presence of HA under our experimental conditions. The results also indicated that HA enhanced the Co(II) sorption at low pH, but reduced the Co(II) sorption at high pH. It was hypothesized that the significantly positive influence of HA at low pH on the Co(II) sorption on γ-Al₂O₃ was attributed to strong surface binding of HA on γ-Al₂O₃ and subsequently the formation of ternary surface complexes such as ≡S-OOC-R-(COO⁻) _x Co^2−x . Chemi-complexation may be the main mechanism of the Co(II) sorption on γ-Al₂O₃ in the presence of HA.     

Factors affecting the sorption of Eu(III) on modified silica gel</p> </p>

Summary 8-Hydroxyquinoline in benzene, xylene, chloroform and toluene diluents was used to modify silica gel as a solid phase extractant (SPE) for the sorption of Eu(III) in batch extraction techniques. Influences of solid/liquid ratio, pH, metal ion concentration, particle size and temperature were studied. The optimum initial pH is 4.2, while the maximum sorption capacities for the prepared impregnated resins in benzene, xylene, chloroform and toluene diluents are 18.52, 14.98, 14.79 and 5.94 mg ^. g^-1, respectively. The sorption process is found to be affected by both metal ion concentration and particle size of the impregnated resin. Thermodynamic parameters for the sorption of Eu(III) were determined and the reaction is found to be exothermic and spontaneous with enthalpy-14.23 and-23.71 kJ ^. mol^-1 for benzene and xylene as diluents. Release of the element from the loaded solid particles into 0.01M HNO₃ is@85% and@53% from 8-HQ/benzene/silica gel and 8-HQ/xylene/silica gel.</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>     

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>     

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>     

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

Summary Diffusions of⁸⁵Sr,¹³⁷Cs,⁶⁰Co and¹²⁵I radionuclides have been studied in borecore samples from Boda siltstone/claystone formation (BCF) under ambient and in situ conditions. In-diffusion (⁸⁵Sr,¹³⁷Cs,⁶⁰Co and¹²⁵I) and through-diffusion measurements (¹²⁵I) were performed at ambient conditions, and for iodine, in-diffusion measurements were also carried out at in situ conditions (100 bar, 50 °C). In the case of cationic species carrier-containing solutions were also applied.⁶⁰Co was detected only in the first slice of borecore at each sample, while¹³⁷Cs was detected also in the first-, second- and third slices according to the concentration-increase of inactive carrier. Among the investigated cations,⁸⁵Sr exhibited the fastest diffusion rate with 2.7-6.0 ^. 10^-12m²/s apparent diffusivity values. In the course of in-diffusion measurements 4.7 ^. 10^-11 m ² /s, during through-diffusion investigations 1.4-1.6 ^. 10^-12m²/s and at in situ conditions 5.0-8.0 ^. 10^-12 m²/s apparent diffusivities were obtained for¹²⁵I.Modest sorption of¹²⁵I can also be deduced from the results.</p> </p>     

Sorption and desorption of UO2 2+, Th4+ and Ru3+ on the synthetic analogue of muscovite</p> </p>

Summary Sorption and desorption of UO₂²⁺, Th⁴⁺ and Ru³⁺ on the synthetic analogue of the mica mineral muscovite has been studied by a batch technique. The synthesized gel was characterized by XRD, EDXRFS, FTIR, TGA and SEM and was found to have a composition K_1.4Al_4.2(Si₆Al₂O₂₀)(OH)₄ ^. 2H₂O. Different parameters like acid concentration, contact time, amount of gel, composition of gel: OPC admixture, effect of temperature, desorption of metal ions from loaded muscovite and effect on crystal morphology due to loading of metal ions were studied. The results has been expressed in terms of distribution coefficient (K_d).</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>     

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>     

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>     

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>     

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>     

Investigation of 85Sr adsorption in the presence of Na+, K+ and Cs+ on selected soils from different horizons</p> </p>

Summary Results of studies of Na⁺, K⁺ and Cs⁺ influence on the adsorption of ⁸⁵Sr on soil samples of the different types of successive horizons are presented. It was proved that the adsorption isotherms in log-log coordinates are of straight-line type and may be described by the Freundlich equation. Monovalent cations influence the coverage degree of the soil surface by ⁸⁵Sr (most often lowering it) in the following order K⁺3Na⁺3Cs⁺. The investigation of pH influence proved its essential meaning in the process. The plateau of surface coverage degree versus pH lies above pH 5.5 or 6.5 depending on the soil type. Generally, in the studied system, the size of ⁸⁵Sr adsorption depends on the concentration of the isotope, pH of the solution, type of monovalent cation, and on the soil properties.</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>     

Fundamental issues of the effective decontamination of the steam generators of Paks NPP</p> </p>

Summary During the period of 1993-2001 chemical decontaminations of 24 SGs in the units 1-3 of the Paks NPP were carried out by a non-regenerative version of AP-CITROX technology, even in two or three consecutive cycles. A comprehensive investigation of the above decontamination method have revealed that the fundamental issues of analytical chemistry and corrosion science were not taken into consideration during the elaboration of AP-CITROX procedure. Therefore, the non-regenerative version of the technology utilized at Paks NPP can be considered to be not an adequate method for the chemical decontamination of any reactor equipments having large steel surfaces (e.g., SGs). As a consequence of the lack of the appropriate decontamination method, initiation of a R&D project focused on the elaboration of the required technology should not be postponed. In this paper, we present a brief overview on the fundamental issues of the technology development. Selected findings obtained in our laboratory on the field of the improvement of the AP-CITROX technology are also reviewed in order to demonstrate the crucial role of some selection criteria.</p> </p>