Sequential separation and determination of plutonium, americium-241 and strontium-90 in soils and sediments

A sensitive and reliable metbod for the sequential separation and determination of plutonium,²⁴¹Am and⁹⁰Sr in soil samples was developed. Plutonium was separated by a Microthene-TNOA column. Then⁹⁰Y (for⁹⁰Sr determination) was separated from americium by a HDEHP column after elimination of large amounts of interfering stable or radioactive nuclides (iron,²¹⁰Bi and²¹⁰Po etc.) by an oxalate precipitation and a Microthene-TNOA column. Finally americium was purified by another HDEHP column and a PMBP-TOPO extraction. A special attention was paid to the decontamination of Pu and Am from²¹⁰Po and of⁹⁰Y from²¹⁰Bi; the relevant decontamination factors resulted greater than 10⁵, 10⁶ and 10⁴ respectively. The detection limits were 1.2 mBq/kg for Pu and 1.7 mBq/kg for²⁴¹Am and 0.32 Bq/kg for⁹⁰Sr. The procedure was checked by analyzing three certified samples supplied by IAEA. Some Italian soil samples were also analyzed giving average yields of 84.9±7.2% for Pu, 57.8±3.2%for Am and 96.7±1.6% for Y; the^239+240Pu,²³⁸Pu,²⁴¹Am and⁹⁰Sr contents (Bq/kg) ranged from 0.347 to 1.53, from 0.013 to 0.048, from 0.126 to 0.556 and from 2.89 to 11.6 respectively and the average ratios were 0.037±0.017 for²³⁸Pu/^239+240Pu, 0.357±0.040 for²⁴¹Am/^239+240Pu and 7.0±1.2 for⁹⁰Sr/^239+240Pu.     

Measurement of 90Sr in Marine Biological Samples

Strontium-90 (⁹⁰Sr) is one of the most hazardous radionuclides, and it contributes to radiation exposure by ingestion. The routine determination of ⁹⁰Sr in marine biological samples is highly desirable given the development of the nuclear power industry. A fast, simple, and low-detection-limit method was developed for the measurement of ⁹⁰Sr in marine biological samples based on determining ⁹⁰Y by means of coprecipitation and solvent extraction with bis-2-ethylhexyl-phosphoric acid (HDEHP) in n-heptane. The interfering ²¹⁰Bi is removed using Bi₂S₃ precipitation. The separation and purification of eight samples per day can be accomplished through this method. The detection limit of ⁹⁰Sr for this method is 0.10 Bq/kg (ash weight). The radiochemical procedure was validated by fitting the decay curve of the sample source and by the determination of ⁹⁰Sr standards.     

89Sr/90Sr-Determination in soils and sediments using crown ethers for Ca/Sr-separation

A radiochemical procedure is described for the sensitive determination of⁸⁹Sr and⁹⁰Sr activity concentrations in soil and sediment samples. After leaching the sample with hydrochloric acid, Sr is separated from most of the soluble matrix constituents and Ca by solvent extraction using dicylclohexano-18-crown-6 in trichloromethane. After backextraction with a EDTA-solution (ethylene diamine tetra acetate), Sr is purified by several precipitation steps from traces of matrix constituents and radionuclides which might interfere the beta measurements of⁸⁹Sr,⁹⁰Sr and⁹⁰Y. The detection limits are about 0.2 Bq/kg and 0.4 Bq/kg for⁹⁰Sr and⁸⁹Sr respectively. The procedure can be applied to all kind of environmental samples with small modifications of the sample preparation steps prior to analysis.     

The importance of separation chemistry for the determination of radionuclides in environmental samples

Separation chemistry plays an important role when alpha-and beta-emitting natural and artificial radionuclides at low levels must be determined in complex environmental matrices. This paper describes some separation techniques used in radioecology, with special emphasis on extraction chromatography. The very high necessary decontamination factors are pointed out together with the suggested techniques. The following examples are given: (a) determination of⁹⁰Sr in soils in the presence of high concentration of²¹⁰Bi; (b) determination of cosmogenic³²P in sea water and its decontamination from²³⁴Th; (c) determination of⁶³Ni and⁵⁹Ni in liquid effluents; (d) separation techniques used for the speciation of plutonium in sea sediments and (e) plutonium and²⁴¹Am concentration and vertical distribution in mosses.     

Determination of90Sr by thin layer radiochromatography

A simple method for the determination of⁹⁰Sr by using thin layer chromatography on silica gel or cellulose pretreated with calcium oxalate is proposed. In these conditions a complete separation between strontium and its daughter yttrium is obtained. Radioactivity of separated elements was measured by a linear multiscanner analyzer and the results were computer processed to obtain the activity of⁹⁰Sr. The method has been applied to samples of water and milk subjected to a very simple extraction procedure. Under the experimental conditions used, the detection limit is about 25 mBq of deposited radioactivity, which corresponds to about 6 Bq/l.     

Environmental radioactivity in Romania Danube river area during 1986–1990

This paper presents the results of radioactivity studies of environmental factors such as surface water, sediment, aquatic vegetation and soil. The concentrations of¹³⁷Cs,⁹⁰Sr,³H, U, Ca, and Mg in water samples were determined by radiochemical and chemical methods. Gamma-spectrometric analyses were performed for all the samples. The analysis showed a decrease in concentrations of¹³⁷Cs in water, aquatic vegetation and sediment, but a constant level of¹³⁷Cs activity in soil (0–5 cm depth). The average concentrations of⁹⁰Sr,³H, U, Ca and Mg were about 7 mBq/l, 11 Bq/l, 0.6 g/l 60 mg/l and 11 mg/l, respectively.     

Determination of 90Sr in soil, grass and cereals

⁹⁰Sr was measured in environmental samples in Upper Austria in the year 2005. After the nuclear weapon tests the average deposition of ⁹⁰Sr in Austria amounted to 3.3 kBq/m². In 1986 the average deposition was 0.9 kBq/m² [1]. To assess the actual condition in soil, grass and cereals ⁹⁰Sr was measured in these samples. For all samples oxalate precipitation was conducted and strontium specific columns (Eichrom Industries, Inc.) were used. The calcium concentration in these samples was determined to estimate the amount of resin needed for the preparation. For grass and cereal samples columns were packed with the 100–150 μm resin to gain a lower limit of detection LLD below 2 and below 0.1 Bq/kg_{dry matter} respectively. The prepacked 2 mL columns with particle size 100–150 μm were used for soil (LLD below 2 Bq/kg_{dry matter}). After digestion of soil samples, hydroxide precipitation was used as an additional separation step. The ⁹⁰Sr was measured by liquid scintillation counting. For quality control reasons, first the initial strontium concentration in the sample was determined then a strontium carrier solution was added and after the separation steps the chemical recovery was determined by ICP-MS. Thus, no radioactive tracer and just a small amount of the measuring solution were needed. The results are presented and discussed. These results will be used as reference for further ⁹⁰Sr analyses which will be conducted in a 5 year period to detect any radiological impact of the nuclear power plant Temelin on the environment of Austria.     

Separation of the radioelements210Pb−210Bi−210Po by spontaneous deposition onto noble metals and verification by Cherenkov and liquid scintillation counting

A method for the separation of²¹⁰Pb,²¹⁰Bi and²¹⁰Po using spontaneous deposition has been developed. The²¹⁰Bi and²¹⁰Po are simultaneously removed by deposition onto nickel foil (copper and tin could also be used but less effectively) while the²¹⁰Po is separated from²¹⁰Bi, after dissolution of the nickel foil, by deposition onto silver foil. The effectiveness of each separation was evaluated by adding aliquot portions of each solution to a cocktail and counting with a liquid scintillation counter. Water was used as the medium to observe the Cherenkov count of the sample solution.     

Separation of radioactive strontium from natural samples by means of mixed-solvent anion exchange

A new procedure for isolation and determination of⁹⁰Sr in real natural samples is presented. It consists of bringing natural samples in a soluble form suitable for separation on an ion-exchange column, separation of calcium from strontium by means of the anion exchanger Amberlite CG-400 and 0.25M HNO₃ in methanol as eluent for calcium, and the determination of⁹⁰Sr using a low level -counter after elution with H₂O, scavenging steps and SrCO₃ precipitation. The method was tested with IAEA standards of natural samples with known contents of⁹⁰Sr, and water samples, where the concentration of⁹⁰Sr was previously determined by the standard IAEA procedure. The results obtained show that it is possible to isolate and determine low levels of⁹⁰Sr in natural samples. The procedure is favorable because of the simple separation of radioaactive strontium without using fuming nitric acid.     

Strontium-90 determination in biological and environmental samples by direct milking of its daughter product, yttrium-90

A method is presented for the determination of ⁹⁰Sr in environmental samples by direct milking of ⁹⁰Y. Pyridine-2,6-dicarboxylic acid forms an anionic complex with yttrium which is retained on an anionic resin. Most of the matrix elements are washed out of the column as neutral or uncomplexed species and yttrium is eluted by increasing the ionic force of the eluent solution. This method gives yttrium recoveries between 65% to 85% for soil, grass, milk and bone samples with very high radiochemical purity (⁹⁰Y average half-life of 66±4 hours) and a detection limit of 0.3 Bq/kg of soil. The method supports a calcium content up to 3 g per sample without any decrease in yttrium yield, allowing the measurement of milk, milk-teeth and bone samples with no concentration step in one day.     

89,90Sr fallout from Chernobyl in the Bucharest-Magurele area

⁸⁹Sr and⁹⁰Sr were determined in the fallout of May 1986. The maximum values of 335 Bq/(m².6 h) and 110 Bq/(m².6 h) were observed on May 2 and 5. Throughout May 1986 a quantity of 860 Bq/m² of⁹⁰Sr, deposited from the fallout in the Bucharest-Mgurele area, was estimated.     

90Sr and137Cs in fallout from Chernobyl in the Bucharest-Măgurele area during 1986–1987

This work shows the variation of⁹⁰Sr and¹³⁷Cs in atmospheric fallout in the Bucharest-Mgurele area during 1986–1987. The amount of⁹⁰Sr in the fallout was estimated to be about 900 Bq.m^–2 in 1986 and about 9.2 Bq.m^–2 in 1987. The amount of¹³⁷Cs was estimated to be 13300 and 615 Bq.m^–2 in 1986 and 1987, respectively.     

Determination of210Pb in sediments by extraction chromatography

A selective method is described for the determination of²¹⁰Pb in sediments, based on the separation of the daughter²¹⁰Bi by extraction chromatography with Microthene 710-tri-n-octylphosphine oxide (TOPO) and on a final source counting with a low background -counter. The average chemical yield is 92.0%. The detection limit for 2 g samples is 19 Bq kg^–1. An IAEA reference sediment sample was analyzed to check the reliability of the method.     

Separation of Ba and Pb from aqueous solutions of Sr with commercially available “precipitated active manganese dioxide”

Ba and Pb radionuclides can be removed from Sr in aqueous solution in both sodium acetate and acetic acid, containing 20 mg Sr carrier, by stirring with small (0.1–0.5 g) amounts of solid manganese dioxide. In tracer experiments⁸⁵Sr was separated with only small losses from¹³³Ba and²¹⁰Pb by separation factors of 87 and 135, respectively. The separation factor is defined here as the % of the initial⁸⁵Sr activity/ % of the initial¹³³Ba or²¹⁰Pb activity remaining in the aqueous phase after MnO₂ contact. The applicability of this technique for removing Ba and Pb radionuclides in the analysis of⁹⁰Sr in environmental samples (especially milk) is discussed.     

Determination of technetium-99 from the aspect of environmental radioactivity

A radioanalytical procedure has been developed for the determination of⁹⁹Tc in environmental samples. The procedure consists of precipitation, solvent extraction, ion exchange, electrodeposition and radiation measurement. Rhenium was used as a non-isotopic carrier of⁹⁹Tc. On the basis of 3σ counting error, the detection limits were 4.9·10^?5 Bq/l, 7.4·10^?3 Bq/kg wet and 7.4·10^?2 Bq/kg dry for water, biota and soil samples, respectively. Sea water, seaweeds (brown algae) and soils were collected to evaluate the present levels of⁹⁹Tc in Japan. The level of⁹⁹Tc in sea water was ca. 1·10^?4 Bq/l around Japan. Among the seaweeds (brown algae), Ishige okamurai showed the highest concentration of 5.8·10^?2 Bq/kg wet tissue and the highest concentration factor of 583. The level of⁹⁹Tc in the organic rich surface soil was ca. 1 Bq/kg dry soil in Fukuoka.     

Rapid determination of 89,90Sr in wide range of activity concentration by combination of yttrium, strontium separation and Cherenkov counting

The methodology for the rapid determination of ^89,90Sr in wide range of activity concentration is given. Methodology is based on simultaneous separation of strontium and yttrium from samples by mixed solvent anion exchange chromatography, mutual separation of ^89,90Sr from ⁹⁰Y by hydroxide precipitation and quantitative ^89,90Sr determination by Cherenkov counting within 3 days. It is shown that Y and Sr can be efficiently separated from alkaline, alkaline earth and transition elements as well as from lanthanides and actinides on the column filed by strong base anion exchanger in nitrate form and 0.25 M HNO₃ in mixture of ethanol and methanol as eluent. Decontamination factor for Ba, La and other examined elements except calcium is low and can not affect quantitative determination in predictable circumstances. Methodology for quantitative determination by Cherenkov counting based on following the changes of sample activity over time is described and discussed. It has been shown that ^89,90Sr can be determined with acceptable accuracy when ⁸⁹Sr/⁹⁰Sr ratio is over 10:1 and that separation of Y enables reliable determination of ⁸⁹Sr and ⁹⁰Sr in wide range of ⁸⁹Sr/⁹⁰Sr ratios (60:1) and in some cases in presence of other yttrium and strontium isotopes. The methodology was tested by determination of ^89,90Sr in Analytics crosscheck samples (nuclear waste sample) and ERA proficiency testing samples (low level activity samples). Obtained results shows that by using of low level liquid scintillation counter it can be possible to determine ⁸⁹Sr and ⁹⁰Sr in wide range of concentration activity (1–1,000 Bq/L/kg) with uncertainty below 10% within 2–3 days. Results also show that accuracy of determination of ⁸⁹Sr (and ⁹⁰Sr) strongly depends on the determination of difference between separation and counting time when activity ratio of ⁸⁹Sr/⁹⁰Sr is high. Examination the influence of media and vial type on background radiation and counting efficiency has shown that lowest limit of determination can be obtained by using of HNO₃ in plastic vials as counting media, because in this combination figure of merit is maximized. For the recovery of 50% and 100 min of counting time estimated MDA is 55 Bq and 90 Bq for ⁹⁰Sr and ⁸⁹Sr, respectively. Analysis of combined uncertainty shows that it mainly depends on uncertainty of efficiency and recovery determination, uncertainty of activities determination for both isotopes and level of background radiation.     

Studies of 90Sr concentration and migration in the soils of the Łęczna-Włodawa Lake District

Research data on concentration and transportation of ⁹⁰Sr in cutivate soils and its migration in undisturbed from Łęczna-Włodawa Lake District are presented. ⁹⁰Sr analysis was based on yttrium path. A special attention was paid to the precision in excluding of Th and U radioisotopes and their daughters using solid-liquid extraction (on Dovex ionite), and Pb by PbI₂ precipitation. The obtained results revealed various contamination of studied soils by ⁹⁰Sr although its concentration did not exceed 10 Bq/kg in the most samples. The highest concentration was noticed in upper 20 cm layers in both types of soils. Vertical migration rate of ⁹⁰Sr, calculated from compartment model, was below 1 cm/yr for the most researched soils.     

Liquid scintillation spectrometry of beta-emitters in marine samples

Liquid scintillation spectrometry has become the most widespread method for quantitative analysis of low level -emitters in environmental samples. This technique has been applied in the measurements of ²⁴¹Pu, ³H and ⁹⁰Sr in seawater and sediment samples. ²⁴¹Pu can be measured by direct analysis of an electrodeposited source using - discrimination or by extraction of electrodeposited plutonium into a liquid form compatible with scintillation cocktail. Sediment from Mururoa and Fangataufa atolls showed activities ranging from 18 to 44 Bq/kg. A sediment profile sampled around Bikini Atoll in 1997 showed ²⁴¹Pu activities ranging from 0.3 to 30 Bq/kg. ³H activities in pore water sediment from Mururoa and Fangataufa atolls were of the order of 10³ Bq/m³ which demonstrated its underground origin. ⁹⁰Sr was measured in the presence of ⁹⁰Y. The counting efficiency was 92.41.5% and the background 0.027±0.001 s^-1. The average chemical recovery for ⁹⁰Sr was 673%.     

Simultaneous determination of210Bi and210Po on pine needles by solvent extraction and liquid scintillation counting

A determination procedure has been developed for²¹⁰Bi and²¹⁰Po in environmental samples and was applied for pine needles. Bismuth-210 and²¹⁰Po separated from the parent nuclide²¹⁰Pb as BiOCl precipitate were extracted simultaneously by TOPO/toluene containing PPO and POPOP. The separation of²¹⁰Bi and²¹⁰Po from²¹⁰Pb was almost satisfactory. The activity of²¹⁰Bi+²¹⁰Po in the TOPO/toluene was measured periodically by liquid scintillation counting for about 20 days after separation. The time course of the decreasing pattern of the activity was determined by the initial activity ratio²¹⁰Po/²¹⁰Bi. The decreasing pattern of the activity was compared with theoretical patterns, and best estimates for²¹⁰Po and²¹⁰Bi were obtained by non-linear least-squares fitting. The activities of²¹⁰Bi and²¹⁰Po were determined for one-year and two-year old pine needles fro the same pine tree, and weathering half-time and deposition rate of these nuclides was discussed.     

Ceric phosphate as ion exchanger in the separation of carrier-free210Bi from210Pb,90Y from90Sr and UX1 from u

Separations of tracer cations in parent daughter systems such as carrier-free²¹⁰Bi from²¹⁰Pb,⁹⁰Y from⁹⁰Sr and UX₁ from U have been carried out in a column of ceric phosphate as ion exchanger. The exchanger has been prepared by mixing ceric sulfate in hot 10M orthophosphoric acid at 80°C and keeping for overnight. A pale yellow coloured precipitate was formed which was washed, dried at 70°C for 48 hours when a hard, granular variety suitable for column use, with a cerium to phosphate ratio of 1∶2 was obtained. 0.1M H₃PO₄ was used as medium in each of the systems studied. The β-decay curves of the separated²¹⁰Bi and⁹⁰Y and the γ-spectrum of UX₁ show that all these activities are radiochemically pure. The separation procedures adopted in each case were very clean and simple, gave quantitative yields and took less than half an hour.