This paper describes the processes used at the Fukushima Daiichi plant, Japan, to purify the waste effluents generated in the cooling of damaged reactors. These include primary cesium removal with the Kurion zeolite system and the SARRY system utilizing silicotitanate to remove radiocesium from water recirculated to reactors for cooling. Another process is the ALPS system to purify the retentates of the reverse osmosis plant to further purify the water from radionuclides after primary cesium separation. In ALPS, a major role is played by the transition metal hexacyanoferrate product CsTreat and sodium titanate SrTreat in the removal of radiocesium and radiostrontium, respectively. The performance of these four exchangers (zeolite, silicotitanate, hexacyanoferrate, and sodium titanate) is critically analyzed with respect to processing capacities and the decontamination factors obtained in the processes. Furthermore, general information on preparation, structure and ion exchange of these ion-exchanger categories is given with additional information on their use in nuclear waste effluent treatment processes. Finally, the importance of selectivity and associated factors are discussed.

For the modeling of cesium sorption on biotite, samples of natural biotite separated from gneissic rocks were converted into monoionic potassium, sodium, and calcium forms, and sorption isotherms for Cs/K, Cs/Na and Cs/Ca exchange were determined at pH 6 and 8 in E-4–E-8 M Cs solutions. Selectivity coefficients for Cs/K, Cs/Na, and Cs/Ca ion exchange reactions were calculated from the isotherm data, using the Gaines-Thomas convention. At Cs loadings below 1% of the total ion exchange capacity, the overall selectivity coefficient for Cs/Ca exchange was approximately five and seven orders of magnitude higher than those for Cs/Na and Cs/K exchange, respectively. Based on the selectivity coefficients, the ion exchange isotherms were modeled with the U.S. Geological Survey PhreeqC program, assuming three different types of ion exchange site: sites on the basal planes on biotite crystal surfaces with 95% site abundance, probable interlayer sites on crystal edges [frayed edge sites (FESs)] (0.02%) and third-type sites (5%), the physical background of which is unclear. Of these three types, the FES sites were superior in Cs selectivity, while the planar sites exhibited the lowest selectivity, and the third-type sites had selectivity between these two. The functionality of the model was successfully verified by modeling the Cs sorption isotherms on crushed mica gneiss rock in saline groundwater. Determination of the exchangeable ions K, Na, Ca, and Cs on the basal plane and edge surfaces by scanning electron microscopy-energy-dispersive x-ray spectroscopy (SEM-EDX) supports the results of modeling: edge sites highly prefer Cs ions and also Ca and Na ions but not K ions.