Removal of137Cs from an intermediate level liquid waste by using various ion-exchange media

An intermediate level liquid waste (ILLW or Category III waste) stream was treated for the removal of radioactive Cs in pilot scale experiments, using three different ion exchange media. Results indicated that the polyacrylic fibre coated with cupric ferric hexacyanoferrate (CuFeHCF-fibre composite) was the most efficient, followed by cupric hexacyanoferrate loaded ion exchange resin (CuHCF-resin) and mixed zeolites (AR-1, 4A and 13X in the ratio 6:1:1). The mixed zeolites column and the CuFeHCF-fibre column were used in series in order to get a high total decontamination factor (DF). Leaching studies on the CuFeHCF-fibre composite loaded with¹³⁷Cs, in demineralised (DM) water, tap water and ground water media indicated a release of about 19.3%, 25.5% and 41.3% of¹³⁷Cs, respectively, in a period of about 8 months. XPS studies with CuFeHCF-fibre composite indicated some chemical interaction between the CuFeHCF precipitate and the polyacrylic fibre. Some of the possible disposal options for the CuFeHCF-fibre composite have also been discussed.     

Application of Cu·FeHCF coated acrylic fibre for the separation of Cs isotopes in drinking water to determine fallout 137Cs

Ten fresh water samples of wells and rivers from the environment of Tarapur Maharashtra Site were analyzed to evaluate and establish the fall out level of ¹³⁷Cs activity concentration using large volume of water samples. A radiochemical separation method suitable for the analysis of large volume of water sample based on the adsorption of Cs isotopes on coated acrylic fibres was standardized. ¹³⁴Cs isotope was used for monitoring the radiochemical recovery of the analysis. Radiochemical recovery was obtained in the range of 74?C98% for a sample volume of 250?L or more. The fall out level ¹³⁷Cs concentration in river/dam water was found to be in the range of 0.205 to 0.268?mBq?L^?1. The fall out level annual effective dose through water ingestion pathway for a member of public was evaluated to be 2.27?×?10^?9?Sv.     

Extraction of cesium in seawater off Japan using AMP-PAN resin and quantification via gamma spectroscopy and inductively coupled mass spectrometry

The March 2011 earthquake off the Japanese coast and subsequent tsunami that devastated the Fukushima Dai-Ichi nuclear power plant resulted in the largest accidental release of cesium 137 and 134 to the oceans. Seawater samples were collected in June 2011 from 30 to 600 km off the coast of Japan as part of initial mapping of the spread of contamination in the ocean. Cesium was extracted from unfiltered and filtered (<1.0 μm) seawater using an absorber based upon an organic polymer polyacrylonitrile (PAN) containing ammonium molybdophosphate (AMP) Sebesta and Stefula (J Radioanal Nucl Chem 140:15–21, 1990). The AMP-PAN resin can be counted directly using gamma spectroscopy for ¹³⁴Cs and ¹³⁷Cs. Stable ¹³³Cs was added to evaluate extraction efficiency and quantified by ICP-MS. Our 5 mL AMP-PAN resin column was on average 95 % efficient in the removal of cesium from 20 L samples at an average flow rate of 35 mL min^?1. Measured activities of ¹³⁴Cs and ¹³⁷Cs ranged from a few Bq m^?3 to >300 Bq m^?3. The extraction column can be adapted to different sample volumes and easily used in the field.     

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.     

Evaluating the residence time for cesium removal from simulated Hanford tank wastes using SuperLig® 644 resin

Batch contact and column experiments were performed to evaluate the effect of residence time on cesium removal from two simulated Hanford tank wastes using SuperLig^® 644 resin. The two waste simulants mimic the compositions of tanks 241-AZ-102 and 241-AN-107 at the U.S. Department of Energy (DOE) Hanford site. A single column made of glass tube (2.7-cm i.d.), which contained ~100 ml of H-form SuperLig^® 644 resin was used in the column experiments. The experiments each consisted of loading, elution, and regeneration steps were performed at flow rates ranging from 0.64 to 8.2 BV/h for AZ-102 and from 1.5 to 18 BV/h for AN-107 simulant. The lowest flow rates of 0.64 and 1.5 BV/h were selected to evaluate less than optimal flow conditions in the plant. The range of the flow rates is consistent with the River Protection Project design for the waste treatment plant (WTP) columns, which will operate at a flow rate between 1.5 to 3 BV/h. Batch contact experiments were also performed for two batches of SuperLig^® 644 to determine the equilibrium distribution coefficients (K _d) as a function of Cs concentration. The column experiments revealed that adequate column loading for Cs on SuperLig^® 644 (50% breakthrough at 100 bed volumes) can be achieved for the two simulated Hanford tank wastes at the nominal plant flow rates of 1.5 and 3 BV/h (residence times 40 and 20 minutes). The column performance was marginally improved at flow rates below the nominal rates. At flow rates higher than the nominal, the Cs loading deteriorated significantly. The SuperLig^® 644 was eluted effectively with 0.5M nitric acid. The elution required approximately 15 BVs to reduce Cs concentration to below 1% of initial Cs concentration in the feeds.     

Performance of immobilized moss in the removal of 137Cs and 90Sr from actual low-level radioactive waste solutions

The efficiency of immobilized moss as a bio-sorbent for the removal of ¹³⁷Cs and ⁹⁰Sr radionuclides from actual low-level radioactive waste (LLW) solutions was investigated. Preliminary batch experiments with the moss (Funaria hygrometrica) for the sorption of Cs and Sr have shown a pH dependent binding trend from pH 1–13, with maximum binding between pH 5–10. Time dependence of the batch studies showed that a contact time of 30 minutes was sufficient to reach equilibrium. Column experiments for the sorption of Cs and Sr by moss after immobilizing in polymer silica matrix demonstrated that the sorbent is capable of removing considerable amounts of Cs and Sr from actual LLW solutions under constant flow conditions. The adsorption capacity was estimated to be 8.5 mg/g for Cs and 15 mg/g for Sr. These sorbed metal ions from the column could be leached out using 0.20M nitric acid. The regenerated sorbent exhibited relatively the same initial binding capacity of both Cs and Sr even after 3 cycles of reuse. This revised version was published online in July 2006 with corrections to the Cover Date.     

Development of a method for nuclide leaching from glass fiber in HEPA filter

For the disposal of the high efficiency particulate air (HEPA) glass filter to environment, the glass fiber should be leached to lower its radioactive concentration. To derive the optimum method for removal of Co and Cs from HEPA glass fiber, four methods were applied in this study. Results of electrochemical leaching of glass fiber by 4.0 M HNO₃–0.1 M Ce(IV) solution showed that the removal efficiency of ¹³⁴Cs, ¹³⁷Cs, and ⁶⁰Cs from glass fiber after 5 h was 96.4, 93.6, and 93.8%, respectively. Results by 5 wt% NaOH solution showed that the removal efficiency of ¹³⁴Cs, ¹³⁷Cs, and ⁶⁰Cs after 30 h was 81.7, 82.1, and 10.0%, respectively. Results by repeat 2.0 M HNO₃ solution showed that the removal efficiencies of ¹³⁴Cs, ¹³⁷Cs, and ⁶⁰Cs after 2 h of three repetitions were 96.2, 99.4, and 99.1%, respectively. Finally, results by repeat 4.0 M HNO₃ solution showed that the removal efficiencies of ¹³⁴Cs, ¹³⁷Cs, and ⁶⁰Cs after 4 h of three repetitions were 100, 99.9, and 99.9%, respectively, and their radioactivities were below 0.1 Bq/g. Therefore, the chemical leaching method by 4.0 M HNO₃ solution was considered as an optimum one for removal of cesium and cobalt from HEPA glass fiber for self disposal. Also the removal efficiencies of ⁶⁰Co, ¹³⁴Cs, and ¹³⁷Cs from the waste-solution after its precipitation-filtration treatment for reuse of 4.0 M HNO₃ waste-solution were 88.0, 95.0, and 99.8%.     

Synthesis and characterization of ammonium molybdophosphate–silica nano-composite (AMP–SiO2) as a prospective sorbent for the separation of 137Cs from nuclear waste

The ammonium molybdophosphate–silica (AMP–SiO₂) nano-composites were prepared by sol–gel method. The material synthesized was nanocrystalline, with average crystallite size of primary particles in the range of 10–25 nm. Small angle X-ray scattering showed presence of mass fractal aggregates made of small particles with rough pore boundaries. To realize the scope of using AMP–SiO₂ nano-composites sorbent for removal of ¹³⁷Cs from nuclear waste solutions, its adsorption characteristics for cesium were evaluated. It was found that the AMP–SiO₂ nanocomposites were amenable for column operation, have high affinity for Cs, and possess very high adsorption capacity for Cs. From the perspective of separation of ¹³⁷Cs from acidic radioactive waste solution, AMP–SiO₂ nanocomposite holds significant promise.     

Separation of cesium-137 from uranium fission products via a Neoflon® column supporting tetraphenylboron

Cesium is a member of the Group I alkali metals, very reactive earth metals that react vigorously with both air and water. The chemistry of cesium is much like the chemistry of neighboring elements on the periodic table, potassium and rubidium. This close relation creates many problems in plant-life exposed to cesium because it is so easily confused for potassium, an essential nutrient to plants. Radioactive ¹³⁴Cs and ¹³⁷Cs are also chemically akin to potassium and stable cesium. Uptake of these radioactive isotopes from groundwater by plant-life destroys the plant-life and can potentially expose humans to the radioactive affects of ¹³⁴Cs and ¹³⁷Cs. Much experimental work has been focused on the separation of ¹³⁷Cs from uranium fission products. In previous experimental work performed a column consisting of Kel-F supporting tetraphenylboron (TPB) was utilized to separate ¹³⁷Cs from uranium fission products. It is of interest at this time to attempt the separation of ¹³⁴Cs from 0.01M EDTA using the same method and Neoflon in the place of Kel-F as the inert support. The results of this experiment give a separation efficiency of 88% and show a linear relationship between the column bed length and the separation efficiency obtained.     

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.     

Temporal variation of 137Cs inventory in the western North Pacific

The temporal variation of water column inventories of ¹³⁷Cs in the western North Pacific was examined. ¹³⁷Cs in seawater of the western North Pacific has originated mainly from global fallout from atmospheric nuclear weapons tests, which occurred in the early 1960's. In the western North Pacific, the water column inventories of ¹³⁷Cs were 5200 Bq·m^-2 in 1973 (GEOSECS station GX225) and 3400 Bq·m^-2 in 1983 (KH-84-3 station AN-1). In 1997, the ¹³⁷Cs inventory was 2600 Bq·m^-2 at station 1 of the IAEA'97 cruise. The global fallout at Tsukuba since 1945 was estimated to be 5600 Bq·m^-2 in 1973, 4600 Bq·m^-2 in 1983 and 3500 Bq·m^-2 in 1997. The water column inventories of ¹³⁷Cs were 93–74% of the estimated global fallout for the same latitude. The typical features of the temporal variation for three vertical profiles taken in 1973, 1983 and 1997 are the decrease of ¹³⁷Cs activity in the mixed layer and the gradual increase of ¹³⁷Cs activity in deeper layers. The proportion of the ¹³⁷Cs inventory in waters down to 1000 meters was 100% in 1973, 88% in 1983 and 75% in 1997. These findings suggest that large amount of the ¹³⁷Cs entering through sea surface would remain in the mixed layer for more than a few decades.     

Temporal variations of137Cs concentrations in the surface seawater and marine organisms collected from the Japanese coast during the 1980's

The surface seawater and marine organisms were collected on the Japanese coast and analyzed for their¹³⁷Cs concentrations during the 1980's. The¹³⁷Cs concentrations in surface seawater decreased almost exponentially with time and the¹³⁷Cs removal rate constant was estimated to be 0.0445 y⁻¹. The¹³⁷Cs concentrations in marine organisms also decreased almost exponentially with time. The environmental half-lives of¹³⁷Cs in muscle and viscera of fish, crustacea, and seaweed were estimated from the measured decreases of¹³⁷Cs concentrations.     

Effect of temperature on SuperLig® 644 cesium removal from simulated Hanford tank waste supernate

Batch kinetic and column experiments have been carried out at 25, 35, and 45 °C to examine the effect of temperature on SuperLig® 644 cesium (Cs) removal from simulated Hanford tank waste supernate. The simulated solution mimicked the composition of the low-activity waste supernate from tank 241-AN-105 in the U.S. DOE Hanford site. Small quantities of toxic metals, such as Cd, Cr, Fe, and Pb were spiked into the simulant to evaluate the metal's competitiveness with Cs for sorption on SuperLig® 644 resin. The results indicated that the temperature affects the removal of Cs and metal ions, although the effect was not the same for all metal ions. The extent of Cs removal decreased with an increase in temperature. The Cs capacity at breakthrough point was 0.015, 0.013, and 0.011-mmole/g dry resin at 25, 35 and 45 °C, respectively. The column was effectively eluted to less than 1% (0.1 C/C ₀) of the feed concentration with approximately 10 BVs of 0.5M nitric acid. The resin showed limited affinity for toxic metal ions (Cr, Cd, Fe, and Pb) as compared to Cs. Based on the batch kinetic data, the Cs uptake of the resin was not hampered by the presence of the toxic metals in solution.     

Utilization of low-cost sorbent for removal and separation of 134Cs, 60Co and 152+154Eu radionuclides from aqueous solution

Eggshell material was used as low-cost and eco-friendly biosorbent for removal of ¹³⁴Cs, ⁶⁰Co and ^152+154Eu radionuclides from aqueous solution. The eggshell material was calcined at 500 and 800 °C, and then characterized. Comparative studies on the natural and calcined eggshell for sorption of the three radionuclides were carried out. It was found that, the uptake is in the order: Eu(III) > Co(II) > Cs(I). Further, column chromatography was used in separation of ¹³⁴Cs, ⁶⁰Co and ^152+154Eu using 0.15, 0.2 and 0.5 mol/l nitric acid, respectively. Eggshell material can be considered as a promising material for separation of radionuclides from radioactive waste solution.     

Iron-modified light expanded clay aggregates for the removal of arsenic(V) from groundwater

Iron modified materials have been proposed as a filter medium to remove arsenic compounds from groundwater. This research investigated the removal of arsenate, As(V) from aqueous solutions by iron-coated light expanded clay aggregates (Fe-LECA). Arsenic is effectively adsorbed by Fe-LECA in the optimum pH range 6-7 by using a 10 mg mL^− 1 adsorbent dose. Kinetics experiments were performed to investigate the adsorption mechanisms. Electrostatic attraction and surface complexation were proposed to be the major arsenic removal mechanisms. The experimental data fitted the pseudo-first-order equation of Lagergren. For an arsenic concentration of 1 mg L^− 1, the rate constant (k₁) of pseudo-first-order was 0.098 min^− 1, representing a rapid adsorption in order to reach equilibrium early. Equilibrium sorption isotherms were constructed from batch sorption experiments and the data was best described by the Langmuir isotherm model. Large scale column experiments were conducted under different bed depths, flow rates, coating duration and initial iron salts concentration to determine the optimal arsenic removal efficiency by Fe-LECA column. Volumetric design as well as higher hydraulic detention time was proposed to optimize the efficiency of the column to remove arsenic. In addition, concentrated iron salts and longer coating duration were also found to be crucial parameters for arsenic removal. The maximum arsenic accumulation was 3.31 mg of As g^− 1 of Fe-LECA when the column was operated at a flow rate of 10 mL min^− 1 and the LECA was coated with 0.1 M FeCl₃ suspension for a 24 h coating duration.     

Investigation of adsorption and vertical migration of137Cs in three kinds of soil at Lublin vicinity

The results of field, column and laboratory studies carried out on three types of mineral soils are encloses presented. Based on the field tests, average migration rates of¹³⁷Cs were calculated. The highest rate was found for the brown soil (FAO/UNESCO—Cambisol). Cesium migrated with the lowest rate in the podzol soil (FAO/UNESCO—Cambic Podzol). The column experiments confirmed the above observation. In laboratory tests the adsorption and desorption isotherms of Cs were determined on samples taken from 0–2 cm layers of each soil profile. It was found from the calculated partition coefficients that Cs is always irreversibly bonded to some extent, but it appears to be completely and irreversibly immobilized on the podzol soil. The permanent retention of cesium in the podzol soil was also confirmed by microcalorimetric studies. The desorption energy was negligibly small and amounted to −0.21 mJ/g. In the brown soil, containing prevailing amounts of loamy minerals, the desorption energy was found to be 106.89 mJ/g. The investigations are supplemented by the sorption kinetics measurements. These indicate that the adsorption equilibrium is reached after a dozen, up to twenty or so minutes.     

The interaction mechanisms between aqueous solutions of137Cs and134Ba radionuclides and local natural zeolites for an deactivation scenario

¹³⁷Cs and¹³⁴Ba were removed from synthetic aqueous solutions by means of natural zeolites of Slovakian origin. The equilibrium sorption behavior of Cs and Ba ions onto clinoptilolite and mordenite were studied under static as well as dynamic experimental conditions. Both Freundlich and Langmuir isotherms describe satisfactory by Cs and Ba adsorption on the zeolites studied. The elution of Cs and Ba ions from zeolite columns after the loading cycle was undertaken additionaly, in order to compare column operating runs of various exchanged zeolite forms.     

Separation of bulk Y from 89Y(n,p) produced 89Sr by extraction chromatography using TBP coated XAD-4 resin

⁸⁹Sr was produced using the ⁸⁹Y(n, p) ⁸⁹Sr reaction by irradiating yttria target in the fast breeder test reactor (FBTR). An analytical scale procedure was standardized for the removal of the bulk target yttrium by solvent extraction using the tri-n-butyl phosphate (TBP). The final purification of ⁸⁹Sr source was carried out by ion exchange chromatography. However, extraction chromatography is preferred to solvent extraction due to its low waste generation and ease of operation. This paper reports the separation of Sr from bulk Y and other radioactive impurities produced during irradiation by extraction chromatography using TBP coated XAD-4 resin. Initially the separation procedure was standardized using ⁸⁵Sr and ⁸⁸Y tracers. The ⁸⁹Sr in the dissolver solution of the irradiated yttria target was separated under the same standardized conditions. The study established the separation of Sr from Y in the dissolver solution of the irradiated target yttria by the TBP coated XAD-4 column. However the evaluation of the column after every use for about three separation studies exhibited the reduction in its breakthrough capacity for yttrium.     

Comparison of food processing retention factors of 137Cs and 40K in vegetables

Removal of radiocesium from food by processing is of great concern following the accident of TEPCO’s Fukushima Daiichi Nuclear Power Plant accident. To provide more Cs removal rates, we studied the applicability of K data using edible plant samples. Values were compared for ¹³⁷Cs and ⁴⁰K of the food processing retention factors, F _r (total activity in processed food/total activity in raw food), and they were found to be close to the 1:1 line and highly correlated (R = 0.96, p < 0.001). Thus, K can be an analogue to estimate radiocesium removal rates by food processing of vegetables. Using the literature K values, we calculated the K removal rates (%), that is, (1 ? F _r) × 100, for ten vegetable types to provide potential Cs removal rates. The average percent of K removal were as follows: dried pulses, 33; fresh pulses, 15; leafy vegetables, 52; fruit vegetables, 7; flower vegetables, 44: root crops, 18; tubers, 16; ferns, 93: mushrooms, 32; and others, 30.     

Mass selective separation applied to radioisotopes of cesium

A technique that uses the intrinsic mass‐based separation capability of a quadrupole mass spectrometer has been used to resolve spectral radiometric interference of two isotopes of the same element. In this work the starting sample was a mixture of ¹³⁷Cs and ¹³⁴Cs and was (activity) dominated by ¹³⁷Cs. This methodology separated and ‘implanted’ ¹³⁴Cs that was later quantified for spectral features and activity with traditional radiometric techniques. This work demonstrated a ¹³⁴Cs/¹³⁷Cs activity ratio enhancement of >4 orders of magnitude and complete removal of ¹³⁷Cs spectral features from the implanted target mass (i.e. 134). Copyright © 2016 John Wiley & Sons, Ltd.