Radiochemical analysis of radionuclides difficult to measure for waste characterization in decommissioning of nuclear facilities

Some radiochemical analytical methods for the determination of important beta-radionuclides for decommissioning are presented. An analytical method is briefly described, which is used for the determination of ³H and ¹⁴C in steel and aluminum by combustion using commercial oxidizer. A leaching method was developed for the determination of ³H in the contaminated silica gel. A simple distillation method is presented for the determination of ¹⁴C in heavy water and wastewater sample. A method developed for the simultaneous determination of ³H, ¹⁴C, ³⁶Cl, ⁵⁵Fe, ⁶³Ni, ⁴¹Ca and ¹²⁹I in concrete, graphite, aluminium, lead, and steel is presented. The developed methods have been successfully used to analyse various materials for characterization of the waste during the decommissioning of Danish nuclear reactors.     

Simultaneous determination of nitrogen and lithium by thermal neutron activation analysis

The determination of lithium and nitrogen in a variety of materials by thermal neutron activation is described. The nuclear reactions used are ¹⁴N(n,p)¹⁴C and ⁶ Li(n,α)³H. Radionuclides. ¹⁴C and ³H for counting are isolated by fusion of the irradiated sample in a vacuum system. Data are presented on lithium and nitrogen concentrations in several terrestrial standards. The new method allows reliable measurements on 10–50-mg samples.     

A novel method for the simultaneous determination of125I and14C activities using liquid scintillation counting

The viability of a dual label liquid scintillation technique has been investigated. To avoid the need for two procedures, gamma counting for¹²⁵Iodine (¹²⁵I) and liquid scintillation counting for¹⁴C. Since the¹²⁵I spectrum covers almost as wide a range of pulse heights as¹⁴C, conventional dual label methods would result in very low¹⁴C counting efficiencies. The conventional dual label technique has ben modified to increase the¹⁴C counting efficiency and to accomodate the consequent additional spillover of¹²⁵I counts into the upper window. This dual label technique has been applied to the determination of¹²⁵I and¹⁴C activities in blood samples. The accuracy of the method has been tested, and its advantages and limitations are discussed.     

Liquid scintillation assay of 3H and 14C-labelled polymers

The assay of a range of ³H and ¹⁴C-labelled polymers by liquid scintillation counting is reported. Methods of sample preparation such as combustion, solution, gelation and suspension techniques are described and compared. The validity of a variety of procedures of counting efficiency determination for the above methods is examined and critically discussed.     

Possibilities of the determination of3H,14C and131I individually and in mixtures,by the method of amplitude attenuation using liquid scintillators

Possibilities of the determination by radioactivity measurements of³H,¹⁴C and¹³¹I are described for the individual nuclides and their mixtures, with the use of liquid scintillators. The changes in the counting efficiency have been determined as a function of the parameters of the measuring equipment, and parameters are suggested which make possible the determination of³H,¹⁴C and¹³¹I individually, or in the pairs³H−¹⁴C,³H−¹³¹I,¹⁴C−¹³¹I, and finally, in the triplet³H−¹⁴C−¹³¹I.     

A simple and reliable monitoring system for 3H and 14C in radioactive airborne effluent

Summary A simple and reliable sampling system for ³H and ¹⁴C in airborne release from nuclear facilities was designed. The sampling system can collect ³H and ¹⁴C simultaneously with a condensation technique using a commercially available cold trap equipment and a CO₂ absorption technique using an organic alkali monoethanolamine solution, respectively. In situ performance tests for the effluent from a reprocessing plant showed that the system has high and stable efficiencies for collecting ³H and ¹⁴C for a one-week batch sampling at a sampling flow rate of 0.4 l ^. min^-1. These collection techniques also provided a simple procedure of following sample preparation for activity measurements by liquid scintillation counting. The detectable concentrations of the proposed monitoring method were 3.0 Bq ^. m^-3 for ³H and 1.6 Bq ^. m^-3 for ¹⁴C, respectively. The sensitivity would be on an acceptable level for routine monitoring of airborne release at nuclear facilities.     

Oxidation-liquid scintillation radioassay of phenolics from cellulose thin-layer chromatography plates

A new technique is described for the radioassay of ¹⁴C labeled phenolics removed from thin-layer chromatographic plates using cellulose nitrate solution. Samples are transferred to liquid scintillation vials for direct oxidation and ¹⁴CO₂ absorption preparatory to counting. High-efficiency counting results are recorded for the low-activity-level phenols with and without selective chromagenic spray detection. The method includes greater economy, and superior sample preparation and handling characteristics as advantages over other methods currently in use.     

Simultaneous determination of35S and14C in double-labelled organic compounds by liquid scintillation counting

An isotope analytical method for the simultaneous determination of³⁵S and¹⁴C in double-labelled organic compounds by liquid scintillation counting is described. The sample is burned in a stream of oxygen. Sulfur oxides are converted to sulfuric acid and separated from other combustion products, including carbon-14 dioxide, on a heated quartz wool column previously wetted with hydrogen peroxide. Carbon dioxide is collected from the gas stream by an absorbent suitable for liquid scintillation counting. The residual sulfuric acid is rinsed off the column with water and the aqueous solution obtained is mixed with a liquid scintillation cocktail for radioactivity measurement. The final solutions ready for counting are obtained in less than fifteen minutes, quantitative collection recovery is achieved and no cross contamination occurs.     

Design and performance of a miniature TDCR counting system

A portable liquid scintillation counting system based on the triple-to-double coincidence ratio (TDCR) method was developed at Sofia University “St. Kliment Ohridski”. The system consists of a miniature TDCR counter with cylindrical optical chamber and a specialized TDCR counting module named nanoTDCR. The nanoTDCR module is produced by the labZY company and provides several important new TDCR counting functionalities like: individual extending-type dead-time in each channel; simultaneous counting with two different extendable dead-times and two different coincidence windows and simultaneous TDCR counting and spectrum acquisition. The performance of the new system was tested in benchmark comparisons with the LNHB’s primary TDCR counting system of activity measurements of ²⁴¹Am, ³H, ¹⁴C and ⁶³Ni. Good agreement between the two systems was observed.     

Study of kinetics,equilibrium and isotope exchange in ion exchanger systems

An automatic, rapid combustion method has been developed for the determination of tritium and¹⁴C in singly or doubly labelled organic materials by liquid scintillation counting. The sample is burned in a stream of oxygen. The water formed and its tritium content are retained from the gas stream in an absorber containing a small amount of diethyleneglycol monoethyl ether. Radioactive carbon dioxide, if included in the combustion products, is transferred into 3-methoxypropylamine. The final solutions ready for counting are obtained in less than three minutes. Quantitative collection recoveries for both tritium and¹⁴C are achieved and no cross-contamination occurs.     

Simple measurement of14C in the environment using a gel suspension method

A simple analytical method for environmental¹⁴C with a low background liquid scintillation counter was developed. We used a new gelling agent, N-lauroyl-L-glutamic-α,γ-dibutylamide, for the liquid scintillation counting of¹⁴C as CaCO₃ (gel suspension method). Our procedure for sample preparation was much simpler than that of conventional methods and required no special equipment. The samples prepared with the standard sample of CaCO₃ were measured to evaluate the self absorption of the sample, the optimum condition of counting and the detection limit. Our results indicated that the newly developed technique could be efficiently applied for the monitoring of environmental¹⁴C.     

Vergleich der Meßgenauigkeit der Szintillations-Zählung 3H- und/oder 14C-markierter Proben durch externe bzw. interne Standardisierung und Anwendung auf die Sauerstoff-Kolben-Verbrennung

After oxygen flask combustion scintillation samples often show an increase in counting rates for several hours. Even after such a time identically prepared samples are statistically significantly more different as one should expect by weighing and pipetting errors. The inconstant cpm values during the first hours and the differences between the samples can mostly be eliminated by quench correction curves (dependence of counting efficiency and external channel ratio upon oxygen concentration). The dpm values achieved according to this method show smaller standard deviations than by internal standardisation. The procedure of the external standardisation was examined for error propagation. A system of toluene/methanol/phenethylamine absorbs carbon dioxide and water quantitatively. With this mixture the following counting efficiencies are achieved: 25% for ³H, 85% for ¹⁴C and for samples containing ³H and ¹⁴C 15% for ³H and 10% for ¹⁴C if the ³H channel is adjusted according to Klein and Eisler.     

Measurement of uranium in small quantities in phosphates by use of γ-ray spectrometry and the 1001 keV peak of <Superscript>234m</Superscript>Pa

Phosphates, naturally containing trace amounts of uranium, were examined using direct γ-ray spectrometry. Both normal and Compton-suppressed counting modes were utilized. The 1001 keV photo peak of the second daughter of ²³⁸U was chosen because of its isolation from other, potentially interfering peaks. The findings suggest that with the aid of Compton suppression, it is possible to quantify low uranium levels in phosphates using samples sizes of order 10 grams within an accuracy of 5%. The uranium content was determined in several sample types and was found to range from 60±4 to 70±8 μg/g, depending on the sample composition. This investigation also considered the effects of sample size, counting time, and counting technique as sources of precision maximization. This work has shown that only a small amount of phosphate is needed to determine the constituent concentration, instead of the standard several hundred grams of material.     

Simultaneous liquid scintillation determination of239Pu and241Am in tissue

A liquid scintillation counting method for the simultaneous determination of Pu and Am, with a two-phase cocktail, has been applied to the analysis of a tissue sample from an accidental exposure incident. The sample contained²³⁹Pu,²⁴¹Pu, and²⁴¹Am. In addition to analysis by two liquid scintillation counting techniques, analysis of the sample was performed by -spectroscopy and ZnS scintillation techniques, and the results were compared. The presence of²⁴¹Pu interfered with the liquid scintillation determination of²⁴¹Am when the two-phase cocktail was used, but the results were in agreement sufficient to be useful in determining what course of treatment, if any, might be necessary for the patient.     

Optimization of liquid scintillation counting techniques for the determination of carbon-14 in environmental samples

The goal of this work was to optimize the liquid scintillation counting techniques for the determination of¹⁴C in stack effluent gases and in environmental samples such as biological and air samples. Carbon-14 activities in most environmental samples were measured with the direct CO₂ absorption method. The highest figures of merit were found through the variation of Carbosorb E and Permafluor V ratio, and measurement windows. The best condition was an 1:1 volume ratio. Average 2.35 g of CO₂ was reproducibly absorbed in the 20 ml mixture within 40 minutes. The counting efficiency determined by repeated analysis of NIST oxalic acid standard and the background count rate were measured to be 58.8±1.4% and 1.88±0.06 cpm, respectively, in case of saturated solution. The correction curves of counting efficiency for partially saturated solutions and for saturated solutions with quenching were prepared, respectively. The overall uncertainty of the sample specific activity for near background levels was estimated to be about 7% for 4 hours counting at 95% confidence level. Stack effluent gas samples were measured by a gel suspension counting method. After precipitation of CO₂ in the form of BaCO₃, 140 mg of which was mixed with 6 ml H₂O and 12 ml of Instagel XF. The counting efficiency was measured to be 71.5±1.7% and the typical sensitivity of this technique was about 510 mBq/m³ for a 100 min count at a background count rate of 4.7 cpm. For the benzene counting method measurements were performed with a mixture of 3 ml benzene and 1 ml of scintillation cocktail (5 g of butyl-PBD in 100 ml of scintillation-grade toluene) in a low potassium 7 ml borosilicate glass vial. The counting efficiency and the background count rate were measured to be 64.3±1.0% and 0.51±0.05 cpm, respectively. The long-term stability of samples has been checked for all the counting techniques over a two week period, during which no apparent change in counting efficiency and background level was found.     

Incorporating tritiated water into a 14C-sampling system for quantitative estimation of 14C activity in airborne effluent

The effects of incorporating tritiated water into a ¹⁴C-sampling system in sample preparation and ¹⁴C activity measurement by liquid scintillation counting were investigated. Experiments derived the limit of water content in the prepared sample, and also demonstrated that ¹⁴C activity can be determined without any interference from ³H contamination for a clear-sample solution. The results enabled us to estimate the permissible relative humidity of air required for accomplishing sample preparation and ¹⁴C activity measurement. These showed that for sampling of air with less than the permissible relative humidity, total ¹⁴C activity in airborne effluent can be evaluated accurately without dehumidification of air. This revised version was published online in July 2006 with corrections to the Cover Date.     

Incorporating tritiated water into a 14C-sampling system for quantitative estimation of 14C activity in airborne effluent

The effects of incorporating tritiated water into a ¹⁴C-sampling system in sample preparation and ¹⁴C activity measurement by liquid scintillation counting were investigated. Experiments derived the limit of water content in the prepared sample, and also demonstrated that ¹⁴C activity can be determined without any interference from ³H contamination for a clear-sample solution. The results enabled us to estimate the permissible relative humidity of air required for accomplishing sample preparation and ¹⁴C activity measurement. These showed that for sampling of air with less than the permissible relative humidity, total ¹⁴C activity in airborne effluent can be evaluated accurately without dehumidification of air. This revised version was published online in July 2006 with corrections to the Cover Date.     

Distribution of 14C and 3H in low level radioactive wastes generated by wet waste streams from pressurized water reactors

Summary It is impossible to detect ¹⁴C and ³H by direct methods such as γ-spectroscopy because they are pure b-emitters and thus they are classified as hard to measure nuclides (HTM). In this paper the analysis results of ¹⁴C and ³H in the low level radioactive wastes (LLWs), including spent ion exchange resin, evaporated bottom and sludge are presented. The LLWs were generated by three nuclear power plants (NPPs), in Korea all with pressurized water type reactors (PWRs). A simultaneous separation procedure for ¹⁴C and ³H in LLWs was established by wet oxidation-acid stripping. A liquid scintillation analyzer was used for the measurement of ¹⁴C and ³H. It was found that the recovery of ¹⁴C and ³H was 82-99 and 78-103%, respectively, by wet oxidation-acid stripping with diluted standard solutions. At the lowest injection of ¹⁴C and ³H, i.e., at 1.44 Bq for ¹⁴C and 1.22 Bq for ³H, the minimum detectable activity (MDA) of ¹⁴C and ³H was calculated as 0.88 and 0.78 Bq/g, respectively, for the minimum allowable sample weight, using wet oxidation and 16 wt% H₂SO₄ acid. By the wet oxidation-16 wt% H₂SO₄ stripping method no interfering nuclides were detected in the trapping solution of ¹⁴CO₂ and the distillate of ³H. The activity concentration range of ¹⁴C in the analyzed samples, i.e., spent ion exchange resin, evaporated bottom and sludge, was 0.17-110,000, 8.4-1380 and 0.1-10,006 Bq/g, respectively, and that of ³H in the same was from no detectable to 769, 134-14,383 and 0.7-4820 Bq/g, respectively.     

Evaluation of interferences on measurements of 90Sr/90Y by TDCR Cherenkov counting technique

A study to evaluate conditions affecting the determination of ⁹⁰Sr/⁹⁰Y activities in liquid samples by the triple-to-double coincidence ratio (TDCR) Cherenkov counting technique was conducted. The Cherenkov radiation produced by the ⁹⁰Y beta decay was determined using a commercially available Hidex 300 SL liquid scintillation counter. The interferences of sample geometry, including sample counting vial type and volume composition, and sample colour on the TDCR were investigated. The effects of potentially interfering beta and mixed beta–gamma emitters on the TDCR Cherenkov counting of ⁹⁰Sr/⁹⁰Y activities were also examined. The TDCR values were used to quantify counting efficiencies of ⁹⁰Y under different experimental conditions. The results demonstrated that the Cherenkov counting efficiency of ⁹⁰Y is independent of sample volume and counting vial size. The effect of colour quenching was examined using yellow and brown food-grade dyes. The TDCR correction for colour quenching was found to be effective. An evaluation of counting efficiency of different beta-emitting radionuclides demonstrated that strong gamma emissions can contribute to the Cherenkov counting efficiency. Overall, measured radioactivity values deviated from reference values by ≤7.5 %, which is acceptable for screening applications in emergency situations.     

Determination of polonium-210 in phosphoric acid

Polonium-210 in phosphoric acid has been recognized as a significant source of alpha contamination of processed Si-wafers for memory devices of computer. In the present work, a convenient method was developed for the determination of trace²¹⁰Po in phosphoric acid of high purity. For the determination,²⁰⁹Po was used as a yield tracer. The present method consists of (1) addition of the tracer to 5 ml aliquot of phosphoric acid sample, (2) pH adjustment (to 2) of the sample solution to make up electrolytic solution, (3) electrodeposition for the simultaneous achievement of Po separation and preparation of counting source on stainless-steel disc, and (4) alpha-ray spectrometry. By the developed method, more than 95% of Po was separated from phosphoric acid sample onto counting disc. The minimum detectable radioactivity of²¹⁰Po in 5 ml of phosphoric acid was about 0.03 mBq by counting the electrodeposited alpha-activity for 10 days under a counting efficiency of ≈30%.