Sorption of radionuclides on natural materials

Information about the sorption of radionuclides on natural materials used for cementation of liquid radioactive wastes (RAW) is important for predictions of migration rates of radionuclides in the products of fixation. Cementation process for conditioning liquid RAW uses, besides cement, materials which improve quality of products. In Czechoslovakia technology among these materials are clinoptilolite tuffit, mordenite tuff, tobermorite and fly ash. Liquid RAW issued from nuclear power plants contains the principal radionuclides⁶⁰Co,¹³⁴Cs and¹³⁷Cs, therefore, a sorption study of these radionuclides was carried out. pH of liquid RAW was 12.5–13.7 and salt content ca. 200 g·dm^–3. Results of sorption are given by distribution coefficients. The best results for cesium in those pH region and salt content had mordenite tuff D_Cs=100 dm³·kg^–1 and the worst results had fly ash D_Cs=4.1 dm³·kg^–1. The best results for cobalt in those solutions had tobermorite D_Co=38 dm³·kg^–1 and the worst results had fly ash D_Co=6.9 dm³·kg^–1.     

Influence of plant roots upon the mobility of radionuclides in soil, with respect to location of contamination below the surface

The movement of⁸⁵Sr,¹³⁷Cs,⁵⁴Mn and⁶⁰Co in the 50 cm soil profile was studied with and without the presence of plant roots (triticum aestivum) in order to investigate the influence of roots and depth contamination upon the migration of radionuclides. The water table was maintained manually at 3 cm from the bottom. The physiochemical characteristics (E_h Fe^–2, NH ₄ ⁺ , pH and moisture content) as well as the total and extractable radioactivity were investigated. In the discrete contamination, where the location of contamination varied within the soil profile (0–5, 25–30 or 45–50 cm from the top), the influence of location upon the movement of these radionuclides was also studied. It was found that the changes in the soil physicochemical characteristics influenced the mobility of the four radionuclides. The extractability of⁵⁴Mn and⁶⁰Co was significantly increased in the reducing region of the soil, whereas that of⁸⁵Sr,¹³⁷Cs was not. Plant roots excerted significant effects upon the soil characteristics, via, reducing the E_h pH and moisture content of the soil; increasing the extractability of both⁵⁴Mn and⁶⁰Co from the depth of 35 cm downwards. Radionuclide migration occurred via physicochemical and biological transport. The biological transport via plant roots was of particular importance for¹³⁷Cs. Location of contamination had a significant influence upon the mobility of radionuclides. The migration of radionuclides was in the sequence of contamination in middle>bottom>top. The degree of the influence varied with radionuclides concemed. In the top layer contamination, the rank of the migration from the contamination layers, on the other hand⁵⁴Mn,⁶⁰Co and¹³⁷Cs were more mobile and the movement was:⁸⁵Sr⁵⁴Mn⁶⁰Co>¹³⁷Cs. In the middle and bottom contamination layers, on the other hand,⁵⁴Mn and⁶⁰Co and¹³⁷Cs were more mobile and the movement was⁸⁵Sr⁵⁴Mn⁶⁰Co>¹³⁷Cs. The results provide evidence conceming the soil-root interaction influencing the transfer efficiency of radionuclides from below the soil surface into the human food chain.     

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.     

Determination of <Superscript>137</Superscript>Cs and <Superscript>85</Superscript>Sr transport parameters in fucoidic sand columns and groundwater system

The determination is based on the evaluation of experimentally obtained breakthrough curves using the erfc-function. The first method is founded on the assumption of a reversible linear sorption/desorption isotherm of radionuclides on solid phase with constant distribution and retardation coefficients, whereas the second one is based on the assumption of a reversible non-linear sorption/desorption isotherm described with the Freundlich equation, i.e., with non-constant distribution and retardation coefficients. Undisturbed cores of 5 cm in diameter and 10 cm long were embedded in the Eprosin-type cured epoxide resin column. In this study the so-called Cenomanian background groundwater was used as transport medium. The groundwater containing radionuclides was introduced at the bottom of the columns at about 4 mL h⁻¹ constant flow-rate. The results have shown that in the investigated fucoidic sands: (i) the sorption was in principle characterized by linear isotherms and the corresponding retardation coefficients of ¹³⁷Cs and ⁸⁵Sr, depending on the type of sample, were approximately 13 or 44 and 5 or 15, respectively; (ii) the desorption was characterized by non-linear isotherms, and the retardation coefficients of the same radionuclides ranged between 23–50 and 5–25, respectively. The values of the hydrodynamic dispersion coefficients of these radionuclides varied between 0.43–1.2 cm² h⁻¹.      

Sorption of hafnium on hydrous titanium oxide using radiotracer technique

The sorption of hafnium on hydrous titanium oxide (TiO₂·1.94 H₂O) has been studied in detail. Maximum sorption of hafnium can be achieved from a pH 7 buffer solution containing boric acid and sodium hydroxide using 50 mg of the oxide after 30 minutes shaking. The value ofk _d, the rate constant of intraparticle transport for hafnium sorption, from 0.01M hydrochloric and perchloric acid and pH 7 buffer solutions has been found to be 17 mmole·g^–1·min^–2. The kinetics of hafnium sorption follows Lagergren equation in 0.01M HCl solution only. The values of the overall rate constantK=6.33·10^–2 min^–1 and of the rate constant for sorptionk ₁=6.32·10^–2 min^–1 and desorptionk ₂=2.28·10^–5 min^–1 have been evaluated using linear regression analysis. The value of correlation factor() is 0.9824. The influence of hafnium concentration on its sorption has been examined from 4.55·10^–5 to 9.01·10^–4 M from pH 7 buffer solution. The sorption data followed only the Langmuir sorption isotherm. The saturation capacity of 9.52 mmole·g^–1 and of a constant related to sorption energy have been estimated to be 2917 dm³·mole^–1. Among all the additional anions and cations tested only citrate ions reduce the sorption significantly. Under optimal experimental conditions selected for hafnium sorption, As(III), Sn(V), Co(II), Se(IV) and Eu(III) have shown higher sorption whereas Mn(II), Ag(I) and Sc(III) are sorbed to a lesser extent. It can be concluded that a titanium oxide bed can be used for the preconcentration and removal of hafnium and other metal ions showing higher sorption from their very dilute solutions. The oxide can also be employed for the decontamination of radioactive liquid waste and for pollution abatement studies.     

Assessment of intake of a complex radionuclide bearing dust formed at a nuclear power plant

The aim of this work was to provide an experimental basis for assessing intakes of an industrial actinide-bearing dust from measurements of⁶⁰Co and¹³⁷Cs in the body or urine. Whilst these radionuclides comprised 72% and 19% of the radioactivity present, greater than 90% of the committed effective dose will result from the low concentrations of the actinides present, 0.4%. To assess the dose coefficient for the dust and predict the biokinetics of⁶⁰Co and¹³⁷Cs in workers, absorption parameters for transfer from lungs to blood obtained from an animal study were combined with information on particle deposition and clearance from the ICRP human respiratory tract model and with tissue distribution and excretion data from the most recent systemic models. All other radionuclides were assumed to have Type M absorption characteristics. The dose coefficient for the dust, 1.29·10^–7 Sv·Bq^–1 was estimated to contain 113 kBq⁶⁰Co, 29 kBq¹³⁷Cs and 0.64 kBq of the actinides. The predicted retention and excretion characteristics of⁶⁰Co and¹³⁷Cs in workers after acute or chronic exposure to the dust suggested that measurements of these radionuclides in the body or urine could detect intakes equivalent to a few percent of an annual dose limit of 20 mSv·y^–1.     

Sorption of 14C, 99Tc, 137Cs, 90Sr, 63Ni, and 241Am onto a rock and a fracture-filling material from the Wolsong low- and intermediate-level radioactive waste repository, Gyeongju, Korea

Sorption experiments for radionuclides such as ¹⁴C, ⁹⁹Tc, ¹³⁷Cs, ⁹⁰Sr, ⁶³Ni, and ²⁴¹Am were conducted using two different groundwaters (GM-1 and SS-5) and solid materials (granodiorite and fracture-filling material) sampled from the Wolsong low- and intermediate-level radioactive waste (LILW) repository, Gyeongju, Korea. The distribution coefficients of the radionuclides, K _d’s, were obtained and their sorption properties were discussed for each radionuclide. For all sorbing radionuclides, the K _d values for the fracture-filling material were observed to be higher than those for granodiorite regardless of the groundwater. The K _d values were increased in the sequence ⁹⁹Tc < ¹⁴C < ⁹⁰Sr < ¹³⁷Cs < ⁶³Ni < ²⁴¹Am regardless of sorbent types implying that the sorption of radionuclides onto geological media is affected by their chemical behavior in accordance with geochemical environments. Anionic radionuclides such as ¹⁴C and ⁹⁹Tc showed very low K _d values both for the granodiorite and fracture-filling material. The mineralogical composition of the geological media and groundwater conditions was also observed to be important in the sorption of sorbing radionuclides, especially in the case of strongly sorbing radionuclides.     

Determination of Cd, Co, Cr, Cu, Fe, Mn, Ni and Pb in natural waters, alkali and alkaline earth salts by electrothermal atomic absorption spectrometry after preconcentration by column solid phase extraction

Methods are described for the determination of trace and ultra trace amounts of Cd, Co, Cr, Cu, Fe, Mn, Ni and Pb in natural waters, alkali and alkaline earth salts. Separation and preconcentration of trace metals is achieved by a column solid phase extraction procedure using silica gel modified with derivatives of dithiocarbamates — Na-DDTC (sodium diethyldithio-carbamate and HMDTC (ammonium hexamethylene-dithiocarbamate) as column packing material. The influence of the sorbent preparation procedure on the degree of sorption of the trace analytes is examined for different pH values of the sample solution. Isobutylmethyl ketone (IBMK) is proposed as an effective eluent for quantitative elution of retained metal ions. Optimal instrumental parameters for ETAAS determination of preconcentrated elements in organic eluate are presented. Practical application of sorbents in analysis of natural waters and alkali and alkaline earth salts is demonstrated. Proposed preconcentration procedure combined with ETAAS determination of trace analytes allows the determination of 0.04 g l^–1 Cd, 0.1 g l^–1 Cr, Cu, and Mn and 0.3 g l^–1 Co, Fe, Ni and Pb in natural waters and 1.10^–7% Cd, 3.10^–7% Cr and Mn, 7.10^–7% Co, Ni and Pb and 2.10^–6% Cu and Fe in alkali and alkaline earth salts.     

The validation of a method for determining the migration of trace elements from food packaging materials into food

A new radiotracer method has been developed to measure the migration of trace elements from food contact packaging into four standard food simulants; acetic acid, ethanol, olive oil, deionised water. A sample of material is irradiated in a thermal neutron flux of 10¹⁶n·m^–2·s^–1 to activate the trace elements and produce a range of radionuclides. The sample is then placed in the food simulant and the migration of the radionuclides is monitored by performing -ray spectrometry on a sample of the simulant. Any radionuclides measured must be due entirely to the migration of the elements present in the plastic, since the simulant itself is not radioactive. Preliminary studies have shown that detection limits of around 0.2g·dm^–2 (0.002 mg/kg) can be achieved for antimony in a sample of polyethylene terephthalate. This method can now been extended to measure migration into real foods. This will highlight any differences between the standard simulants currently used and real foods. Since the method only involves irradiation of the packaging material, any food matrix can be studied.     

Thermodynamics of the System HNO3-UO2(NO3)2-H2O at 298.15 K

The sorption of ⁶⁰Co, ⁶⁵Zn, ⁷⁵Se, ¹⁰³Pd, ¹¹⁰Ag and ²⁰³Hg radionuclides by polyurethane foam (PUF) was investigated and optimized with respect to the selection of appropriate sorptive medium, metal, thiocyanate ions (except for ¹¹⁰Ag) and PUF concentration and equilibration time. The influence of common anions and cations on the sorption of each metal was examined. The sorption data subjected to different sorption isotherms have shown that the sorption of all the radionuclides followed Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherms. The sorption capacity intensity and energy were evaluated for each element studied. The variation of sorption with temperature was monitored for all radionuclides except zinc and selenium. The values of H, S and G were estimated and found to be negative indicating exothermic and spontaneous nature of sorption. It was found that PUF is an effective and economical sorbent for traces of metal ions which can be used for the separation/preconcentration of these ions from their very dilute solutions and has useful applications in radioanalytical and environmental chemistry and in radioactive and industrial liquid waste management.     

Determination of137Cs and134Cs in air samples collected near Belgrade /Yugoslavia/ following the Chernobyl accident

This paper presents the results of measurements of¹³⁷Cs and¹³⁴Cs content in air sampled during May 1986. Maximum concentrations:¹³⁷Cs 2.94±0.01 Bq m^–3 and¹³⁴Cs 1.38±0.01 Bq m^–3 were registered on May 3. Several other long lived radionuclides having -energies in the region 33 keV to 1365 keV were registered in the same samples two years later. The results of measurements of the total -activity in air for the same period are also presented.     

Determination of radioisotopes of Ce,Eu, Pu,Am and Cm in low-level-wastes from power reactors

Long-lived isotopes of lanthanides and actinides are very important for the disposal of low-level radioactive wastes. These nuclides serve for risk calculations of accidents. Their determination requires radiochemical separation from high activity main nuclides. Supervision of waste vessels is done by direct non-destructive -spectrometry of the key nuclides:⁶⁰Co for corrosion products and¹³⁷Cs as for fission products as for transuranic elements. The activity ratios of the long-lived nuclides to the key nuclides are called scaling factors. They have to be determined radiochemically in the laboratory in representative samples of each waste type. They are used for activity calculations of long-lived nuclides in the waste vessels. The scaling factors determined are of the order of magnitude of 10^–6 and due to the fact that we have used low-level measurement techniques, we could performe the necessary chemical separations in a laboratory not exceeding the 10-fold free-level limit.     

The uptake of strontium by calcium phosphate phase formed at an elevated pH

The sorption of radioactive strontium by poorly crystalline hydroxyapatite (HA) obtained by the transformation of amorphous calcium phosphate (ACP) at initial pH 10.8, was investigated. Morphological analysis, performed by transmission electron microscopy, has demonstrated that the solid phase consists of nanometer size ultra-micro particles connected into spherical aggregates. A maximum sorption capacity, determined as the asymptote of the sorption isotherm was =(3.8±0.3)·10^–2mol Sr/mol P. Based on this result and the structural conditions, a possible theoretical explanation for the incorporation of a strontium ion into the apatite lattice has been proposed.     

Levels of artificial radionuclides and uranium in rain water collected from Ibaraki (Japan) following the Tomsk-7 accident in Russia

Measurements of some selected radionuclides were carried out in rain waters collected from Ibaraki Prefecture, Japan, following the nuclear accident at Tomsk-7, Russian Federation, in April 1993. The concentrations obtained for artificial radionuclides were⁹⁰Sr1.8 mBq l^–1,¹³⁷Cs0.1 Bq l^–1,¹³¹I0.1 Bq l^–1 and¹²⁹I4 Bq l^–1. Uranium (²³⁸U) concentrations in rainfalls in April 1993 were 6.3–39 ng l^–1. These data were compared to control values obtained previously and there was no appreciable influence on the radioactivity levels in Japan after the Tomsk-7 accident. Since only limited data on the concentrations of¹²⁹I and uranium in rain water are available, these new analytical results contribute to understanding the background levels for these nuclides.     

131I,134Cs and137Cs concentrations in 1986 for some Roumanian foodstuffs

Results of post-Chernobyl measurement on some foodstuff samples /eggs, meat, fruit, honey, medicinal herbs/ from South-Eastern Roumania are presented. Gamma-ray spectrometry was used; the radioactive concentration values are given in nCi.kg^–1 wet weight. A strong decrease in concentrations for eggs from 6–7 May /3.0–7.4 nCi for¹³¹I, 0.25–0.40 nCi for¹³⁴Cs, 0.40–0.85 nCi for¹³⁷Cs per one egg, mainly in the yolk/ to 19–25 May /0.3–1.0 nCi for¹³¹I, 0.15–0.25 nCi for¹³⁴Cs, 0.25–0.40 nCi for¹³⁷Cs/ was observed. The mean values for lamb meat /joint muscle/ were 500 nCi.kg^–1 for¹³¹I, 12 nCi.kg^–1 for¹³⁴Cs, 22 nCi.kg^–1 for¹³⁷Cs /18–25 May/. Relatively reduced values were found for fruits, e.g. compared to dairy products¹. In May–June 1986, the food consumption in Roumania was strictly limited and controlled by competent authorities.     

Determination of the amount and retention efficiency of aerosols arising during the vitrification of medium-level activity wastes from nuclear power plants

During the vitrification of medium-activity liquid wastes simulating the wastes from nuclear power plant aerosols are formed that enter into the gas pumped off from the vitrification furnace. The dependence of solid-aerosol carryover on the parameters characterizing the glass composition and its eluability were investigated in laboratory scale experiments. The aerosol carryover was determined either gravimetrically or radiometrically using radioactive tracers.¹³⁷Cs with a carrier was added to the wastes and the aerosol carryover was determined by following the¹³⁷Cs activity. In the case of the¹³⁷Cs-labeled aerosol it was observed that a higher alkali content in the melted wastes results in a higher carryover of the¹³⁷Cs-labeled aerosol. Using a multicomponent laboratory gas cleaning system a decontamination factor of 6.7·10⁶ was achieved for the removal of the¹³⁷Cs-labeled aerosol from the gas pumped off from the vitrification furnace.     

Determination of cobalt,nickel and copper in steel and in radioactive wastes using desferrioxamine “B”

A simple and sensitive spectrophotometric method for the determination of cobalt, nickel and copper with desferrioxamine-B (desferal) is described. The sensitivity of the colour reactions of cobalt, nickel and copper is increased by introducing desferal. The pH range for the formation of Co II, Ni II or Cu II-desferal. Chelates is 4.5–8.5, 5.5–9, and 6.5–9.5, respectively. The molar absorptivities of the chelates are 1.2·10⁵, 5.6·10⁴ and 4.8·10⁴ at 545 nm, 390 nm and 680 nm, respectively. Beer's law is obeyed up to 10 g/ml of metal ion. The effect of desferal concentration, pH, standing time and interfering ions are discussed. The method was applied to the determination of trace amounts of cobalt, nickel and copper in steel and simulated radioactive wastes.     

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.     

2,3-Dihydroxypyridine-loaded cellulose: a new macromolecular chelator for metal enrichment prior to their determination by atomic absorption spectrometry

New macromolecular chelators have been synthesized, by loading 2,3-dihydroxypyridine (DHP) on cellulose via linkers -NH-CH₂-CH₂-NH-SO₂-C₆H₄-N=N- and -SO₂-C₆H₄-N=N-, and characterized by elemental analysis, TGA, IR, and CPMAS ¹³C NMR spectra. The cellulose with DHP anchored by the shorter linker had better sorption capacity (between 69.7 and 431.1 mol g^–1) for Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Pb(II), and Fe(III)) than the other (51.9–378.1 mol g^–1); the former was therefore studied in detail as a solid extractant for these metal ions. The optimum pH ranges for quantitative sorption (recovery 97.6–99.8%) on this matrix were: 7.0–9.0, 6.0–9.0, 3.0–8.0, 6.0–8.0, 6.0–9.0, 6.0–7.0, and 2.0–6.0 respectively. Desorption was quantitative with 0.5 mol L^–1 HCl and 0.5 mol L^–1 HNO₃ (for Pb). Simultaneous sorption (at pH 7.0) of all metal ions other than Fe(III) was possible if their total concentration did not exceed the sorption capacity (lowest value). The recovery of seven metal ions from their mixture at pH 6.0 was nearly quantitative when the concentration level of each metal ion was 0.2 g mL^–1. The optimum flow rate of metal ion solutions for quantitative sorption of metal onto a column packed with DHP-modified cellulose was 2–7 mL min^–1, whereas for desorption the optimum flow rate for the acid solution was 2–4 mL min^–1. The time needed to reach 50% of the total loading capacity (t_1/2) was <5 min for all the metal ions except Ni and Pb. The limit of detection (blank+3s) was from 0.70 to 4.75 g L^–1 and the limit of quantification (blank+10s) was between 0.79 and 4.86 g L^–1. The tolerance limits for NaCl, NaBr, NaI, NaNO₃, Na₂SO₄, Na₃PO_4, humic acid, EDTA, Ca(II), and Mg(II) for sorption of all metal ions are reported. The column packed with DHP-anchored cellulose can be reused at least 20 times for enrichment of metal ions in water sample. It has been used to enrich all the metal ions in pharmaceutical and water samples before their determination by flame AAS. RSD for these determinations was between 1.1 and 6.9%.     

Environmental radioactivity level in the Ceranavodă area /Romania/ between 1981 and 1983

The environmental factors considered are: surface water, ground water, drinking water, soil, sediment and spontaneous vegetation. The analyses performed showed a low level of radioisotopes. The mean values recorded were: 4.22×10^–3 Bq dm^–3 for¹³⁷Cs, 2.97×10^–3 Bq dm^–3 for⁹⁰Sr, 14.9 Bq dm^–3 for³H and 1.07 g dm^–3 for U, in the Danube waters. The -spectrometric analysies revealed lines corresponding to⁴⁰K and the to the natural decay series of U and Th. There have been also identified the artificial radionuclides¹³⁷Cs and⁶⁰Co in sediment,⁹⁵Zr and⁹⁵Nb in the 1981 vegetation. All artificial isotopes resulted from atmospheric fallout.