Cesium sorption behavior of a mordenite type synthetic zeolite and its modified form obtained by acid treatment

A locally produced mordenite type synthetic zeolite and its modified form obtained by the treatment with dilute hydrochloric acid were tested for their cesium uptake characteristics. The two zeolites were compared with other commercially available synthetic zeolites with respect to their ability to sorb radiocesium from dilute nitric acid solution. The effects of the changes in the composition of the solution including the concentration of nitric acid, sodium and cesium on the uptake of cesium were investigated. The results can be used in the removing processor radiocesium from different types of nuclear plant effluents by these zeolites.     

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.     

Development of prototype titanate ion-exchange loaded-membranes for strontium, cesium and actinide decontamination from aqueous media

We have successfully incorporated high surface area particles of titanate ion-exchange materials (monosodium titanate and crystalline silicotitanate) into porous and inert support membrane fibrils. The resulting membrane sheets were used to evaluate the removal of surrogate radioactive materials for cesium-137 and strontium-90 from high caustic nuclear waste simulants. The membrane supports met the nominal requirement for non-chemical interaction with the embedded ion-exchange materials and were porous enough to allow sufficient liquid flow. Most of the stamped out 47-mm size titanium impregnated ion-exchange membrane discs removed more than 96% of dissolved cesium-133 and strontium-88 from caustic nuclear waste salt simulants.     

Application of magnetite hexacyanoferrate composites in magnetically assisted chemical separation of cesium

Summary Potassium nickel hexacyanoferrate composite with magnetite finds application in the recovery of cesium from low-level liquid waste using magnetic assistance. The apparent sorption capability of hexacyanoferrate-magnetite composite and potassium nickel(II) hexacyanoferrate(II) matched indicating no loss in sorption capability as a consequence of coating to nanoscale magnetite substrate. Selectivity for cesium in a broad pH range, selectivity in the presence of high concentration of sodium nitrate, and fast exchange kinetics are additional features of the nanocomposites.     

Effective Removal of Cesium and Strontium from Radioactive Wastes Using Chemical Treatment Followed by Ultra Filtration

Chemical treatment assumes an important role in the management of radioactive wastes as it is a simple technique and offers advantage in terms of handling of wastes thereby reducing the risk of mansievert exposure. Low level wastes (LLW) and intermediate level wastes (ILW) are generated in various facets of nuclear fuel cycle and have various chemical composition. A systematic study was carried out by using copper ferrocyanide and calcium phosphate precipitation methods for the removal of cesium and strontium, respectively. The supernatants were subjected to ultra filtration (UF) using a membrane having a pore size of 0.2 m. The decontamination factors (DF) at 2 and 24-hour intervals with and without UF were estimated. The DF obtained was in the range of 200–300 for cesium and 200 for strontium with LLW solution which has chemical characteristics similar to ground water. Two hours of settling is adequate for strontium before UF. In case of cesium there is no much change in the DF values by UF. However, the UF has helped in the solid — liquid separation as the flocks of copper ferrocyanide precipitate are feathery in nature. The effect of ionic strength and the presence of TBP on the removal efficiency of cesium and strontium have also been studied. DF are observed to be a function of ionic strength and are low in deionized water, in salt solutions containing 1 to 4M sodium nitrate and also in solutions of ILW. However, increasing the chemical dosing to two times of normal plant dosing has yielded a DF of about 200 for sodium nitrate solutions with respect to cesium removal. When the concentration of ammonium nitrate in the waste exceeds 0.1M, the DF reduces. Entrained TBP as well as soluble TBP reduces the removal efficiency of cesium. This paper deals with the experimental data and mechanism of the processes involved in the removal of cesium and strontium.     

Removal of60Co and134Cs from radioactive process waste water by flotation

The removal of¹³⁴Cs and⁶⁰Co from radioactive process waste water using cetyl pyridinium chloride (CPC) as a collector and cobalt(II) hexacyanoferrate(II) as a precipitant for⁶⁰Co and sorbent (ion exchanger) for¹³⁴Cs was intensively investigated and the best removal conditions could be established. The results indicate that under the optimum conditions removals higher than 96% and 97% could be achieved for Co(II) and Cs(I), respectively. Cobalt(II) hexacyanoferrate(II) was found to have high affinity for cesium and can preferentially remove it in presence of relatively high amounts of other alkali or alkaline earth cations. A two-stage flotation process was successfully tested for the removal of both Cs(I) and Co(II) from waters containing both cations.     

Adsorption of alkali and alkaline earth radionuclides on zeolite from water solutions

The adsorption of cesium and strontium ions from water solutions on zeolite has been investigated in presence of sodium, potassium, magnesium and calcium ions. Distribution ratios of cesium and strontium on the zeolite were determined in solutions of various compositions and solution volume to sorbent weight ratios (batch factor). Breakthrough curves for zeolite layers are reported.     

Sorption-desorption of radiocesium on various sorbents in presence of humic acid

In general, the amount of radiocesium sorbed by the five sorbents with 0.01 mol·dm^–3 NaCl was in order zeolite > NiFeCN–SiO₂ > montmorillonite > aerogel > silica gel. Addition of humic acid solution to the sorbents depressed the sorption of cesium by all sorbents, except for NiFeCN–SiO₂ was not seen, with the greatest effect showing to the aerogel. The presence of humic acid resulted in an enhanced desorption of cesium from zeolite, NiFeCN–SiO₂ and to a lesser extent from montmorillonite and silica gel. The order of cesium retention following desorption for both sorbent and sorbent/humic-acid mixtures was zeolit > NiFeCN–SiO₂ > montmorillonite > silica gel. The presence of humic acid resulted in decreasing of distribution coefficient values for both sorption and desorption processes.     

The mechanism responsible for extraordinary Cs ion selectivity in crystalline silicotitanate

Combining information from time-resolved X-ray and neutron scattering with theoretical calculations has revealed the elegant mechanism whereby hydrogen crystalline silicotitanate (H-CST; H2Ti2SiO7 x 1.5 H2O) achieves its remarkable ion-exchange selectivity for cesium. Rather than a simple ion-for-ion displacement reaction into favorable sites, which has been suggested by static structural studies of ion-exchanged variants of CST, Cs(+) exchange proceeds via a two-step process mediated by conformational changes in the framework. Similar to the case of ion channels in proteins, occupancy of the most favorable site does not occur until the first lever, cooperative repulsive interactions between water and the initial Cs-exchange site, repels a hydrogen lever on the silicotitanate framework. Here we show that these interactions induce a subtle conformational rearrangement in CST that unlocks the preferred Cs site and increases the overall capacity and selectivity for ion exchange.     

Factors affecting interaction of radiocesium with freshwater solids

The paper aims at the analysis of principal factors affecting the interaction of radiocesium with freshwater solids, important for the migration of radiocesium in rivers. Uptake of radiocesium by bottom sediments and suspended solids from small streams was studied as a function of pH and composition of aqueous phase, of the concentration of cesium in water and of the composition of freshwater solids, using laboratory model experiments. pH had negligible effect on the uptake in the pH range 5–9, the uptake decreased at pH values less than 3–5 depending on the nature and concentration of the solids. Addition of cations suppressed the uptake in the order K⁺>Na⁺>Ca²⁺, the suppression began at 0.001, 0.01 and 0.1 mol.dm^?3 concentration, respectively. Increase in cesium concentration in water caused a decrease of radiocesium uptake, but at very low concentrations of cesium combined with higher concentration of sediment (2g·dm^?3) the uptake was independent of cesium concentration. Removal of carbonates, oxidic coatings and organic matter from a sediment did not affect the sorption properties of the sediment. The nature of the effects found confirms that cesium is sorbed mainly by clay components of freshwater solids. Results obtained are compared with literature data and conclusions are drawn on the importance of the factors studied for modelling of radiocesium migration in rivers.     

Highly Crystallized Nanometer‐Sized Zeolite A with Large Cs Adsorption Capability for the Decontamination of Water

Nanometer‐sized zeolite A with a large cesium (Cs) uptake capability is prepared through a simple post‐milling recrystallization method. This method is suitable for producing nanometer‐sized zeolite in large scale, as additional organic compounds are not needed to control zeolite nucleation and crystal growth. Herein, we perform a quartz crystal microbalance (QCM) study to evaluate the uptake ability of Cs ions by zeolite, to the best of our knowledge, for the first time. In comparison to micrometer‐sized zeolite A, nanometer‐sized zeolite A can rapidly accommodate a larger amount of Cs ions into the zeolite crystal structure, owing to its high external surface area. Nanometer‐sized zeolite is a promising candidate for the removal of radioactive Cs ions from polluted water. Our QCM study on Cs adsorption uptake behavior provides the information of adsorption kinetics (e.g., adsorption amounts and rates). This technique is applicable to other zeolites, which will be highly valuable for further consideration of radioactive Cs removal in the future.     

Removal of cesium radioisotopes from solutions using granulated zeolites

The influence of type of zeolite and the flow rate of solution through the column on the removal efficiency of radioactive cesium ions from solution has been investigated. The analysis of the change in the concentration of cesium ions in the solutions and distribution of cesium ions in the column fillings (granulated zeolites), after passing the solutions through the columns filled with various granulated zeolites (zeolite 4A, zeolite 13X, synthetic mordenite) was performed. On the basis of the results of this study, the conditions for the most efficient removal of cesium ions from solutions have been discussed.     

Studies on the feasibility of using crystalline silicotitanates for the separation of cesium-137 from fast reactor high-level liquid waste

The commercially available crystalline silicotitanate inorganic ion exchanger, IONSIV IE-911, and its parent precursor, TAM-5, have been evaluated for the removal of ¹³⁷Cs from nitric acid medium and simulated high-level liquid waste. The distribution coefficient (K _d ) of cesium decreased with increasing nitric acid concentration and at 3.0 M nitric acid, a distribution coefficient of 1150 mL/g and 2600 mL/g were obtained for IONSIV IE-911 and TAM-5, respectively. Rapid uptake of cesium followed by the establishment of equilibrium occurring within three hours. Loading of cesium in ion exchangers increased with the increase in the concentration of cesium in aqueous phase and from Langmuir adsorption model the apparent capacity of cesium was 69 mg/g and 82 mg/g for IONSIV IE-911 and TAM-5, respectively. The performance of the sorbent under dynamic conditions was assessed by following a breakthrough (BT) curve up to C/C _o = 1, where C and C _o are the concentrations of cesium in the effluent and feed, respectively.     

High-temperature oxide melt calorimetry of oxides and nitrides

Thermochemical data for ceramic materials are essential both for understanding fundamental solid state chemistry (structure, bonding, and crystal chemical systematics, as well as vibrational, magnetic, optical, and electronic phenomena) and for predicting phase equilibria, materials compatibility, and reactivity. This Hugh M. Huffman Memorial Award Lecture describes recent advances in high-temperature oxide melt calorimetry in the University of California Davis Thermochemistry Facility and illustrates its application to three problems of technological significance: the relative stability ofα - and β -silicon nitride; the inversion of stability of α - and γ -alumina at the nanoscale, and the ion exchange of cesium and sodium in silicotitanate zeolite-like materials proposed as hosts for radioactive waste.     

Migration of radiocesium in a zeolite-solution system

Some properties of natural zeolite from Zaloka gorica, Slovenia, Yugoslavia were investigated to establish its applicability in solidification and for storage purposes of radioactive waste. It was found that this material is a rather good sorber for cesium, with a capacity of about 0.6 meq g^–1. The migration rate of Cs⁺ in a system ion exchanger-aqueous solution was investigated and correlated with the sorption behaviour of cesium in a system. The leaching rate of cesium from concrete containing zeolite was measured.     

Association of cesium with ferric components in altered flood basalt

Cesium content in eleven positions of a continental basalt with a columnar joint was determined by means of neutron activation analysis. Concentration of cesium is about four times higher at the altered portions of the fracture than at the unaltered. Water and Fe³⁺ content determined by gravimetry, Mössbauer spectroscopy, and inductively coupled plasma optical emission spectroscopy were also correlated with cesium concentration, suggesting accumulation of cesium with ferric components. Such processes may be important for estimating the behavior of radiocesium in the environment.     

Uptake behavior of titanium molybdophosphate for cesium and strontium

This study investigates uptake of cesium and strontium from aqueous solution similar to nuclear waste on three samples of titanium molybdophosphate (TMP) synthesized under various conditions. Effects of concentration of sodium nitrate, pH and contact time on the uptake of cesium and strontium have been studied by bath method. The results showed that TMP has high affinity toward cesium and strontium at pH > 2 and relatively low concentration of sodium nitrate. Kinetic data indicated that cesium uptake process to achieve equilibrium was faster than strontium. Cesium and strontium breakthrough curves were examined at 25 °C using column packed with H₃O⁺ form of TMP and breakthrough curves showed symmetrical S-shaped profiles. At the same time, the calculated breakthrough capacity for cesium was higher than strontium. The results of desorption studies showed that over 99% of cesium and strontium was washed out of column by using 4 M NH₄Cl solution. This study suggests that TMP can have great potential applications for the removal of strontium and specially cesium from nuclear waste solution.     

Extractability of radiocesium from processed green tea leaves with hot water: the first emergent tea leaves harvested after the TEPCO’s Fukushima Daiichi Nuclear Power Plant accident

In some tea tree planting areas within 300 km from the TEPCO’s Fukushima Daiichi Nuclear Power Plant (FNPP), it was found that newly emerged tea plant leaves for green tea contained two radiocesium species (cesium-134 and cesium-137). In this study, using processed green tea leaves for drinking, extraction ratios of radiocesium under several brew conditions were observed. When 90 °C water was used, 50–70% of radiocesium was extracted into the water, while 54–60% of radiocesium was extracted with 60 °C water. A part of radiocesium would be removed from leaves if the leaves were washed with 20 and 60 °C water before brewing, and the efficiencies were 11 and 32%, respectively. Newly emerged camellia leaves were used to simulate the radiocesium removal ratio from raw tea leaves by washing and boiling; radioactivity concentration was decreased to 60% of the original concentration with washing and 10 min boiling. From these results, it was found that almost half of the radiocesium would not be removed from raw or processed tea leaves. The values obtained in the present study could be used for internal radiation dose estimation from tea leaves.     

Fission product separation from seawater by electrocoagulation method

At the Fukushima Daiichi nuclear power station, seawater was urgently injected into the reactor core. Therefore a large amount of seawater containing highly radioactive fission products (FP) accumulated and its treatment has been a serious problem. FP such as Cs, Sr and I in water are generally removed by an ion exchanger such as zeolite and separated with column or chemical precipitation methods. An alternative electrocoagulation method, which efficiently separates fine particles from the liquid phase without a chemical reagent is expected to be part of a useful separation system that can reduce the amount of waste, decrease processing time and simplify the process. In this study, powdered adsorbents, such as ferrocyanide and zeolite, were added to seawater containing simulated FP, and the electrocoagulation effect with Al alloy electrodes were investigated. More than 99 % of Cs and 90 % of I were removed by potassium nickel hexacyanoferrate(II) and silver zeolite, respectively. Sedimentation was promoted by electrocoagulation and addition of an inorganic cohesion promoter further increased the sedimentation rate. Moreover, rapid dissolution reaction with heating of the aggregation substance was not observed, so the thermal risk of aqueous processing of it would be low. In addition, thermal analyses showed that the electrocoagulation process did not lead to thermal decomposition. Therefore, if the electrocoagulation method is applied to a decontamination system, it has the potential to thermally stabilize and reduce waste.