137Cs sorption on granular inorganic ion-exchangers based on titanium and zirconium hydroxophosphates

We have studied the sorption properties of some granular inorganic ion-exchangers synthesized by gel technology, such as titanium and zirconium hydroxophosphates (THP, ZHP), titanium and zirconium molybdophosphates and titanium and zirconium phosphate-ferrocyanides. A high selectivity of THP and ZHP modified with ferrocyanide and molybdate ions to¹³⁷Cs has been found. The possibility of applying inorganic sorbents for the purification of cesium-137 contaminated foodstuff is illustrated on the examples of fish treatment.     

Experimental study and modelling of 137Cs sorption behaviour in the Baltic Sea and the Curonian Lagoon

Sorption–desorption behaviour of ¹³⁷Cs in the Baltic Sea and the Curonian Lagoon was studied in 1997–2009 with the aim to better understand processes responsible for redistribution and sink of ¹³⁷Cs in the system. Data obtained from several sampling campaigns were analyzed and short and long-term kinetic tracer experiments using natural water and bottom sediments were carried out with particles of various sizes from 0.2 to 50 μm. Samples of suspended particles and bottom sediments collected during two sampling campaigns were fractionated according to the size, and association of ¹³⁷Cs with solid phase was studied using sequential extraction. The difference in ¹³⁷Cs behaviour observed between expeditions in 1999 and 2001 was attributed to seasonal variations in chemical composition of suspended particles entering the system and consequent differences between the sorption (in 1999) and the desorption (in 2001) of ¹³⁷Cs in sea water. Data obtained from tracer kinetic sorption experiments with ¹³⁴Cs and bottom sediment fractions of different grain size were used for finding a suitable kinetic sorption model, kinetic constants and the corresponding equilibrium K _d values. It has been found that the modelled data best conform to the mechanism of ion diffusion through the so-called inert layer on the surface of the sediment particles.     

Modeling of the sorption behavior of 137Cs in soils

A model has been used, based on the simultaneous occurrence of the sorption and desorption processes, to describe the sorption behavior of ¹³⁷Cs in soils in Hong Kong reservoir. By fitting the experimental data with a single parameter, relatively constant sorption and desorption rate constants were obtained. The theory also provided an estimate on the number of sorption sites for different masses of soils. Attempts have been made to explain the findings for different types of soils. This revised version was published online in July 2006 with corrections to the Cover Date.     

Sorption characteristics of137Cs onto clay minerals: Effect of mineral structure and ionic strength

The sorption behavior of¹³⁷Cs onto kaolinite, bentonite, illite, and zeolite was studied at different ionic strengths of Na⁺, K⁺, Ca²⁺. A significant effect of ionic strengths on the sorption has been observed. Clay minerals with 21 structure (bentonite, illite) showed much higher sorption than that of 11 structure (kaolinite). Zeolite showed high selectivity for¹³⁷Cs sorption. Sorption behavior of¹³⁷Cs on clay minerals can be explained by their surface charge characteristics originated from mineral structure.     

Characterization of modified clinoptilolite

Samples of clinoptilolite were modified using insoluble hexacyanoferrate from aqueous solution. The modified samples were characterized by elemental analysis, powder X-ray diffraction, solid state NMR and vibrational spectroscopy. The sorption properties of modified clinoptilolite were studied, too. Higher affinity for¹³⁷Cs sorption in comparison with the natural clinoptilolite has been proved.     

Relationships among <Superscript>137</Superscript>Cs, <Superscript>133</Superscript>Cs,and K in plant uptake observed in Japanese agricultural fields

Plant uptake of radiocesium (¹³⁷Cs) was investigated in consideration of the relationships with naturally existing ¹³³Cs and potassium (K). We first determined plant-unavailable fraction of ¹³⁷Cs in soil by batch sorption and sequential extraction methods with a radiotracer. Then, using the data obtained from the batch sorption and extraction methods, we clarified the relationships of plant-available and plant-unavailable fractions between ¹³⁷Cs, ¹³³Cs, and K in soil. Additionally, ¹³⁷Cs concentrations in crop were estimated using ¹³⁷Cs in soil and several factors, i.e. fixation ratio of ¹³⁷Cs in soil, cation exchange capacity, and K concentration in crop. The results implied that the fixation ratio of ¹³⁷Cs in soil was a very important key to understanding ¹³⁷Cs plant uptake.     

Experimental and modeling studies of radiocesium retention in soils

A two-compartment model was used to describe the irreversible sorption behavior of ¹³⁷Cs on frayed edge sites (FES) of finite capacity in soils in Hong Kong reservoir. The sorption rate was assumed to depend on factors like the fractional water activity concentration, the difference between the activity concentration of ¹³⁷Cs in aqueous phase and that in particulate phase, and the number of available sorption sites. By varying the exponents of the different factors, very good fitting was obtained between experimental data and theory. A relationship between the number of available frayed edge sites and the mass of soil was proposed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Studies on new titanium hexacyanoferrate sorbents for radiocesium removal from primary coolant of pressurized water reactors

Recent work directed towards synthesizing and exploring new effective sorbents for radiocesium removal from primary coolants of pressurized water nuclear reactors of the WWER type is presented. Various sorbents synthesized on the basis of titanium hexacyanoferrate are compared with one another from the point of view of their sorption efficiency and stability. The uptake of¹³⁷Cs from solutions containing boric acid and millimolar quantities of ammonium and potassium ions was studied under conditions simulating the process of purification of the coolant bled from the primary circuit of the reactor. A composite-type sorbent was selected of good mechanical properties and negligible solubility, efficiently decontamining large amounts of the solution (considerably exceeding 10⁴ bed volumes) in the course of the column process.     

Mobility of 137Cs Related to Speciation Studies in Contaminated Soils of the Chernobyl Area

Chernobyl derived ¹³⁷Cs present in upper soil layers can still remain available to cation exchange and hence to downward migration. More than its physico-chemical deposit forms (fuel particles and/or condensed aerosols), radiocesium mobility is influenced by soil properties. Although all the soils studied contain illitic clay minerals, different ¹³⁷Cs fixation levels were observed due to: (1) the reactivity state of sorption sites with a low radiocesium content in soil, and (2) the presence, or absence, of organic matter complexes inhibiting cation sorption on clays.     

The sorption behavior of C<Emphasis Type="SmallCaps">s</Emphasis><Superscript>+</Superscript> ion on clay minerals and zeolite in radioactive waste management: sorption kinetics and thermodynamics

In this work, Cs⁺ ion sorption on some clays and zeolite were investigated. ¹³⁷Cs was used as a tracer. Activities were measured with a NaI crystal gamma counter. The particle size distribution was determined by a laser sizer. Surface area of the particles were determined by BET (Brunauer, Emmett and Teller method). Structure analysis was made by using X-ray diffraction. The chemical compositions of the solid samples were determined using a ICAP-OE spectrometer. Kinetic and thermodynamic parameters were determined. Due to very high uptake results; clay and zeolite can be proposed as a good sorbents in waste management considerations.     

Investigation of cesium uptake from aqueous solutions using new titanium phosphates ion-exchangers

The uptake of cesium from aqueous solutions (pH 5) using titanium phosphates was investigated in the absence and presence of background electrolyte (0.1 M NaNO₃) using a batch technique. The determination of cesium was performed by gamma spectroscopy using ¹³⁷Cs as tracer. The obtained sorption isotherms could be satisfactorily reproduced by a Langmuir sorption equation. The maximum uptake capacity values (q _max) calculated fitting the experimental data by this equation were 167 and 118 mg/g for solutions of initial pH 5 in the absence and presence of background electrolyte. Kinetics data obtained at 293, 308 and 323 K could satisfactorily reproduced by the pseudo-second order equation. It was demonstrated that the new synthesized materials can remove considerable amounts of cesium from aqueous solutions and ion exchange is considered to be the principal mechanism for cesium removal. Toxicity characteristic leaching procedure and desorption tests provided data about the application of the sorbents in environmental remediation.     

Extraction of radionuclides from natural waters using alginates

Fourteen samples of wastes from algal plants were tested for possible analytical and/or technological use for⁹⁰Sr and¹³⁷Cs extraction from natural waters. Sorption experiments were carried out in static and dynanic conditions. It was noted that the examined sorbents posses high affinity for Sr²⁺. The sorption capacity reached the value of 4.72·10⁻³ mole/g. Simple and express analytical procedures for⁹⁰Sr determination were developed and tested in the Dnieper estuary region.     

Variability in 137Cs inventories and potential climatic and lithological controls in the central Ebro valley, Spain

The extent of soil erosion in some Spanish semiarid regions has caused great concern regarding the sustainability of soil resources. Accelerated soil erosion, particularly in some Mediterranean areas, is likely to be one of the main environmental problems associated with climate change. Fallout ¹³⁷Cs has been shown to provide a reliable basis for assessing soil erosion rates in different environments around the world. However, existing information concerning the spatial variation of ¹³⁷Cs inventories at reference sites has identified a need for further investigation of the factors affecting their spatial variability in semiarid environments, where stony and skeletal soils are predominant. Reference sites at three locations in the central Ebro valley were selected to investigate the ¹³⁷Cs content of several grain size fractions. Each site included both natural vegetated conditions and cultivated land and the three sites were characterized by different values of mean annual rainfall. The results obtained demonstrate the influence of lithology, land use and climate on the spatial variability of ¹³⁷Cs inventories that increase from 1190, to 1500 and 1710 Bq·m^?2 with increasing annual rainfall values from 300 to 500 mm at the study sites. The soils on marls at the Valareña site had the highest proportion of ¹³⁷Cs in the coarse fractions of cultivated soils (12%) in comparison with soils developed on limestones at Loma Negra (5%), whereas no ¹³⁷Cs content was found in the coarse fractions of soils on glacis-terrace materials at Peñaflor. The ¹³⁷Cs reference inventories are higher in soils on marls and sands at cultivated locations at Valareña and Peñaflor, but have similar values in soils at cultivated and uncultivated locations on limestones at Loma Negra. Therefore, in absence of level undisturbed soils with natural vegetation cover, cultivated flat soils on hard rocks could provide reliable reference inventories.     

Determination of the balance of the nuclear reactor fuel burn-out process by gamma-spectrometry of fission products III

The possibility for the determination of heavy water reactor fuel burn-up on the basis of gamma-spectrometric measurements of the activity quotients¹⁰⁶Ru/¹³⁷Cs and¹³⁴Cs/¹³⁷Cs has been experimentally investigated. The investigation has been carried out on the non-enriched uranium metal fuel of the Czechoslovak Nuclear Power Plant Al. A spectrometer with germanium detector has been used for spectrum analysis of the irradiated fuel gamm-radiation. Burn-up has been determined (1) by the applied here procedure, and (2) from the results of mass-spectrometric determination of the isotopic composition and content of U, Pu and Nd. Two groups of the values obtained have been compared and the influence of the errors of the measured activity quotients on the established deviations has been evaluated.     

Diffusion of 137Cs in compacted bentonite: Effect of pH and concentration

The effect of pH and concentration on the diffusion of ¹³⁷Cs in the compacted bentonite is studied with capillary method at the ionic strength of 0.1M NaClO₄. The apparent diffusion coefficient increases with increasing concentrations if the sorption of radionuclides is largely dependent on the radionuclide concentrations. The apparent diffusion coefficient decreases with increasing pH because most of the radionuclide sorption on the bentonite increases with increasing pH. The interlaminary space contributes significantly to the radionuclide diffusion and sorption in compacted bentonite. The relationship of the apparent diffusion coefficient and the effective diffusion coefficient of ¹³⁷Cs is also discussed.     

Sorption properties of chemically treated clinoptilolites with respect to Cs and Co

The sorption ability of clinoptilolite treated by NaOH solution has been studied. The distribution coefficients of¹³⁷Cs and⁶⁰Co were studied by the radiochemical method. The variation of distribution coefficients with pH was studied. Also the influence of competitive ions on distribution coefficients were investigated. The total cation exchange capacity and XRD analysis were also measured.     

Modes of137Cs desorption from marine sediments by sea water

Sea water is observed to be a good desorbing agent for¹³⁷Cs from marine sediments. Investigations on the sites of¹³⁷Cs binding and their abundance by desorption over extended periods indicated that, whatever the time of contact of sorption,¹³⁷Cs has three modes of desorption: fast component with desorption half-time of 30–50 min, medium component with desorption half-time of 25–50 h and slow component with desorption half-time of 31–112 days. These are expected to be sites of ion exchange, slower exchange and trapped Cs in the clay mineral layer lattices.     

The effect of the synthesis method on the parameters of pore structure and selectivity of ferrocyanide sorbents based on natural minerals

Ferrocyanide sorbents were obtained via thin-layer and surface modification of natural clinoptilolite and marl. The effect of modification method on surface characteristics of these sorbents and their selectivity for cesium was studied. It was shown that the modification resulted in an increase of selectivity of modified ferrocyanide sorbents to cesium as compared with the natural clinoptilolite in presence of Na⁺, as well as in an increase of cesium distribution coefficients in presence of K⁺. The nickel–potassium ferrocyanide based on the clinoptilolite showed the highest selectivity for cesium at sodium concentrations of 10^?4—2 mol L^?1: cesium distribution coefficient was lg K _d = 4.5 ± 0.4 L kg^?1 and cesium/sodium separation factor was α(Cs/Na) = 250. In the presence of NH₄ ⁺, all modified sorbents showed approximately equal selectivity for ¹³⁷Cs. Probable applications of the sorbents were suggested.     

Temporal and spatial variations of <Superscript>137</Superscript>Cs in the waters off a nuclear fuel reprocessing facility in Rokkasho,Aomori, Japan

Five survey cruises were carried out from 2004 to 2007 to determine ¹³⁷Cs concentrations in the water columns off Rokkasho Village, Aomori Prefecture, Japan, where the spent nuclear fuel reprocessing plant of Japan Nuclear Fuel Ltd has been undergoing test operation since March 2006. Seawater samples were collected with a large volume in situ filtration and concentration system at different depths in the water column. ¹³⁷Cs in particulate form could not be detected in the survey area. Dissolved ¹³⁷Cs showed temporal variation, especially in the surface water. Based on the results, it was concluded that no observable ¹³⁷Cs contamination was present in the investigated area. The distribution of ¹³⁷Cs concentrations was influenced by the mixing between the Tsugaru and Oyashio Currents.     

Sorption characteristics of Am(III), Sr(II) and Cs(I) on bentonite and granite

The ability of the back-fill and the host rock materials to take up radioisotopes like ²⁴¹Am, ^85,89Sr and ¹³⁷Cs has been examined as a function of contact time, pH, amount of sorbent, sorbate concentration, and the presence of complementary cations. A batch technique using actual borehole water from the granite formation has been utilized. In general, the uptake of nuclides by bentonite is much higher than that with granite. The sorption order of nuclides on bentonite is Am>Cs>Sr. The presence of complementary cations, Na⁺, K⁺, Ca²⁺ and Mg²⁺ depresses the sorption of Cs and Sr on bentonite. The sorption data have been interpreted in terms of Freundlich and Langmuir isotherm equations. Utilizing the Langmuir isotherm equation, the monolayer capacity, V _m ,and the binding constant, K, have been evaluated. The change in free energy for the sorption of nuclides on bentonite has also been calculated.