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.     

Ion chromatographic separation for analysis of radiostrontium in nuclear reprocessing solutions of high ionic strength

Determination of⁹⁰Sr in nuclear fuel reprocessing solutions can be facilitated by a preparatory separation using analytical ion chromatography (IC). Furthermore, a novel acid suppression system is described which permits IC separation even in the presence of very strong (0.33M) acid. Following acid suppression (where needed), Sr²⁺ is concentrated and separated from most other solution components by selective adsorption on cation concentrator columns. Cation species retained on the concentrator columns with strontium are subsequently separated on a cation IC column. The Sr²⁺ peak aliquot is collected for subsequent radiostrontium analysis by liquid scintillation counting of the beta activity. Results have shown quantitative separation and recovery of strontium. The entire separation system is automated under computer control and is able to handle samples of large (500 ml) and small (l) sizes.     

Rapid determination of radiostrontium in large soil samples

A new method for the determination of radiostrontium in large soil samples has been developed at the Savannah River Environmental Laboratory (Aiken, SC, USA) that allows rapid preconcentration and separation of strontium in large soil samples for the measurement of strontium isotopes by gas flow proportional counting. The need for rapid analyses in the event of a radiological dispersive device or improvised nuclear device event is well-known. In addition, the recent accident at Fukushima Nuclear Power Plant in March, 2011 reinforces the need to have rapid analyses for radionuclides in environmental samples in the event of a nuclear accident. The method employs a novel pre-concentration step that utilizes an iron hydroxide precipitation (enhanced with calcium phosphate) followed by a final calcium fluoride precipitation to remove silicates and other matrix components. The pre-concentration steps, in combination with a rapid Sr Resin separation using vacuum box technology, allow very large soil samples to be analyzed for ^89,90Sr using gas flow proportional counting with a lower method detection limit. The calcium fluoride precipitation eliminates column flow problems typically associated with large amounts of silicates in large soil samples.     

Improved method for the separation of radioactive strontium from various samples by mixed solvent anion exchange

Procedures for the separation and determination of⁹⁰Sr in liquid samples, with cation and anion exchangers have been described. Strontium, yttrium and other cations bind to the cation exchanger and are eluted from the column by means of nitric acid. Separation of yttrium and strontium from other cations is carried out on columns filled with strong base anion exchangers in nitrate form with alcoholic solutions of nitric acid. This separation method enables the determination of⁹⁰Sr through yttrium on a low-level gas flow α, β-counter, as well as through strontium on a lowlevel liquid scintillation counter by means of Cherenkov counting. Such procedures have been tested by the determination of⁹⁰Sr in water, wine, medium radioactive liquid waste samples, milk and clover samples. For comparison, the determination has also been carried out by the standard method. It has been showed that the developed procedures might produce a high efficiency in strontium separation and a satisfactory accuracy of determination.     

Improvements to arapid method for separating strontium from liquid milk by treatment with a chelating resin and crown ethers

In an attempt to improve on a previously reported method¹ for rapidly isolating Sr from liquid milk, the following investigations have been carried out: (1) elution of strontium from a chelating resin with dilute nitric acid, (2) separation of strontium from calcium by extracting from this eluate into chloroform solutions of dicyclohexyl-18-crown-6 (DC18C6), (3) transfer of the strontium into aqueous solution, and (4) removal of barium from this solution by extracting into dichloromethane solutions of 21-crown-7 (21C7). Based on the findings of these studies, a separation scheme was proposed and tested by participating in an interlaboratory comparison on the analysis of⁸⁹Sr and⁹⁰Sr in skimmed milk. The separation scheme requires about 3 hours, provides strontium recoveries greater than 90%, and ensures adequate decontamination factors for the nuclides that occur in milk.     

Rapid trace determination of radiostrontium in milk and drinking water

A rapid method for determining traces of radiostrontium in milk and drinking water is described. The technique involves a batch treatment of the milk sample with a cation exchanger (DOWEX 50W X8) followed by a solvent extraction with a crown ether (DC18C6) and a precipitation of SrCO₃. In the case of water, the strontium is extracted directly with the crown ether. The average separation yield is 74% for milk and 91% for water. The overall separation procedure takes about 8 hours. Activities as low as 0.03 Bq/1 can be determined with a low background GM-counter.     

Speciation of fission products in raw cow milk by high-performance size exclusion radiochromatography

Speciation of fission products (⁹⁰Sr,⁹⁹Tc,¹³⁷Cs and¹⁵²Eu) in raw cow milk was studied using the high-performance size exclusion radiochromatography (HP-SERC) by Biosep-SEC-S® column (Phenomenex, USA). The separation fraction were identified by a UV detector (280 nm) and a scintillation radiodetector. The mobile phase was Jenness-Koops buffer that simulated milk serum. Radiocesium was present only in non-protein fractions. The non-protein fractions complexed 17% of technetium and 57% of strontium. About 32% of strontium and 24% of europium were bound on the high molecular weight proteins (micellar casein). Low molecular weight proteins bound about 11% of strontium and 76% of europium. Non-size effects play a dominant role at HPSERC speciation of technetium, 83% of which follow the lightest fractions of milk.     

Sequential Isotopic Determination of Strontium, Thorium, Plutonium, Uranium, and Americium in Bioassay Samples

A procedure is presented to provide sequential determination of isotopic strontium, thorium, plutonium, uranium, and americium in a single biological sample. The method begins with digestion and dissolution of the sample. Tracers and/or carriers are added to the sample for the purpose of chemical yield monitoring. Strontium is first separated from the actinides and from most of the interfering constituents of the sample by precipitation as carbonates. Strontium isotopes are purified, and ⁸⁹Sr and ⁹⁰Sr are measured by gas proportional counting. Actinides are separated and purified by ion exchange chromatography, co-precipitated with neodymium fluoride, filtered, and counted by alpha-particle spectrometry.     

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.     

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.     

A comparison of classical 90Sr separation methods with selective separation using molecular recognition technology products AnaLig? SR-01 gel, 3M Empore? Strontium Rad Disk and extraction chromatography Sr?Resin

We studied the use of an extraction chromatography for determination of ⁹⁰Sr in contaminated water samples. The aim of our work was to compare selected products from the point of view of the strontium chemical yields and analysis time. Three commercial products, 3M Empore? Strontium Rad Disk, AnaLig^® Sr-01 gel, Sr^®Resin, and two classical methods, liquid?Cliquid extraction with tributhylphosphate and carbonate co-precipitation, were tested for the separation of ⁹⁰Sr. The water sample from nuclear power plant A1 Jaslovske Bohunice was used for radiochemical analysis of ⁹⁰Sr volume activity. Samples were traced with ⁸⁵Sr to monitor strontium chemical recovery and counted either by Cerenkov counting on TRI CARB 2900 TR liquid scintillation counter or low level alpha?Cbeta proportional counter.     

Determination of131I in milk using heterogeneous liquid scintillation counting

Possibilities of the method based on both the selective separation of radioiodine from milk using anion-exchange resin as well as the¹³¹I counting in heterogeneous mixture of this anex with a liquid scintillator are presented. For samples of 4 dm³ volumes, the separation and counting efficiencies about 78% and 45% are achieved. Under the same experimental conditions the background rate is about 0.25 CPS /15 CPM/ and the LLD corresponds to about 7 mBq.dm^–3 /0.2 pCi. dm^–3/.     

The simple radiochemical determination of 90Sr in environmental solid samples by solvent extraction

Determination of ⁹⁰Sr in environmental solid samples is a challenging task because of the presence of so many other radionuclides in samples of interest. This problem was dealt with by radiochemical separation of strontium followed by yttrium separation and Cerenkov counting of the high-energy ??-particle emissions of ⁹⁰Y in order to quantitate ⁹⁰Sr. In this work, an improved method is described for the determination of ⁹⁰Sr in soil samples, through the separation of the daughter ⁹⁰Y at equilibrium. The procedure is based on the HDEHP solvent extraction in combination with liquid scintillation spectrometry (LSS). A low background Quantulus has been optimized for low level counting of Cerenkov radiation emitted by the hard ??-emitter ⁹⁰Y. The analytical quality of the method has been checked by analyzing IAEA Soil-375 reference materials. The analytical method has also been successfully applied to the determination of ⁹⁰Sr for moss-soil samples in inter-laboratory exercises through IAEA??s ALMERA network. The chemical recovery for ⁹⁰Y extraction ranged from 80 to 85% and the counting efficiency was 73% in the window 25?C400 keV.     

Rapid method for determination of radiostrontium in emergency milk samples

A new rapid separation method for radiostrontium in emergency milk samples was developed at the Savannah River Site (SRS) Environmental Bioassay Laboratory (Aiken, SC, USA) that will allow rapid separation and measurement of radiostrontium within 8 hours. The new method uses calcium phosphate precipitation, nitric acid dissolution of the precipitate to coagulate residual fat/proteins and a rapid strontium separation using Sr Resin (Eichrom Technologies, Darien, IL, USA) with vacuum-assisted flow rates. The method is much faster than the previous method that use calcination or cation-exchange pretreatment, has excellent chemical recovery, and effectively removes beta-interferences. When a 100 mL sample aliquot is used with a 20 minute count time, the method has a detection limit of 0.5 Bq·L⁻¹, well below generic emergency action levels.     

Radiological characterization of low-and intermediate-level radioactive wastes

An analytical procedure for the determination of activation products ²³⁸Pu, ²⁴¹Pu, ²³⁹Pu/²⁴⁰Pu, ²⁴¹Am, ²³⁷Np, and a fission product ⁹⁰Sr in radioactive wastes is presented. Samples were decomposed using Fenton’s reaction. The separation was performed by anion-exchange chromatography, extraction chromatography, using TRU and Srresin, and precipitation techniques, followed by α-spectrometry and LSC counting. Tracer solutions and pure ion exchange resins were used to prepare artificial samples and trace nuclides during the analytical procedure. Some real samples of spent ion-exchange resins originating from our TRIGA Mark II research reactor were analyzed.     

Separation and determination of <Superscript>90</Superscript>Sr in low- and intermediate-level radioactive wastes using extraction chromatography and LSC

A methodology for the determination of ⁹⁰Sr in low- and intermediate-level radioactive wastes from nuclear power plants is presented in this work. It is a part of a methodology developed for the sequential radiochemical separation of radionuclides difficult-to-measure directly by gamma spectrometry in these radioactive wastes. The separation procedure was carried out using precipitation and extraction chromatography with Sr Resin, from Eichrom and the ⁹⁰Sr was measured by liquid scintillation counting (LSC). Optimum conditions for the pretreatment, separation and LSC measurements were determined using simulated samples, which were prepared using standard solutions and carriers. The procedure showed to be rapid and achieved a good chemical yield, in the range 60–90%, and a detection limit of 6.0 × 10⁻⁴ Bq g⁻¹. The method was also tested by participation in a national intercomparison program, with aqueous samples, with good agreement of results.     

Determination of radiostrontium in soil samples using a crown ether

A simple and rapid method has been developed for the separation and determination of total radiostrontium in soil. The method consists of three basic steps: oxalate precipitation to remove bulk potassium, chromatographic separation of strontium from most inactive and radioactive interferences utilizing a crown ether (Sr. Spec, EIChroM Industries, Il. USA) and oxalate precipitation of strontium to evaluate the chemical yield. Radiostrontium is then determined by liquid scintillation counting of the dissolved precipitate. When 10 g samples of soil are used, the sensitivity of the method is about 10 Bq/kg. The chemical yield is about 80%. The separation and determination of radiostrontium can be carried out in about 8 hours.     

Determination of radioactive strontium in seawater

This paper describes the procedures of isolating strontium and yttrium from seawater that enable the determination of ^89,90Sr. In one procedure, strontium is directly isolated from seawater on the column filled with Sr resin by binding of strontium to the resin from 3 M HNO₃ in a seawater, and successive elution with HNO₃. In others, strontium is precipitated from seawater with (NH₄)₂CO₃, followed by isolation on a Sr column or an anion exchange column. It is shown that strontium precipitation is optimal with concentration of 0.3 M (NH₄)₂CO₃ at pH = 11. In these conditions, 100% Y, 78% Sr, 80% Ca and 50% Mg are precipitated. Strontium is bound on to Sr column from 5 to 8 M HNO₃, separated from other elements by elution with 3 M HNO₃ and 0.05 M HNO₃. Strontium and yttrium are bound on to anion exchange column from alcoholic solutions of nitric acid. The optimum mixture of alcohols for sample binding is a mixture of ethanol and methanol with the volume ratio 1:3. Strontium and yttrium are separated from Mg, Ca, K, and other elements by elution with 0.25 M HNO₃ in the mixture of ethanol and methanol. After the separation, yttrium and strontium are eluted from the column with water or methanol.In the procedure of direct isolation from 1 l of the sample, the average recovery of 50% was obtained. In the remaining two procedures, the strontium recovery was about 60% for the Sr column and 65% for anion exchange column. Recovery of yttrium is about 70% for the anion exchange column. It turned out that the procedure with the Sr resin (direct isolation and isolation after precipitation) is simpler and faster in the phase of the isolation on the column in comparison with the procedure with the anion exchanger. The procedure with the anion exchanger, however, enables the simultaneous isolation of yttrium and strontium and rapid determination of ^89,90Sr. These procedures were tested by determination of ^89,90Sr on liquid scintillation counter and Cherenkov counting in 5 M HNO₃. Obtained results showed that activity of 50 mBq l⁻¹ of ^89,90Sr and higher can be simultaneously determined.     

Methodology for determination of 89Sr and 90Sr in radiological emergency: I. Scenario dependent evaluation of potentially interfering radionuclides

Early determination of ⁸⁹Sr and ⁹⁰Sr in radiological emergency is hampered by the presence of interfering short-lived fission products. In this study, three commonly used radioanalytical strategies for ⁸⁹Sr and ⁹⁰Sr were evaluated theoretically considering their suitability in a nuclear explosion scenario. The methods were evaluated with respect to the need for decay time of interfering short-lived strontium and yttrium isotopes, and reduction of other known interfering nuclides prior to measurement. The strategy shown to be most successful included initial separation of strontium and determination of ⁸⁹Sr, followed by an yttrium separation and counting of ⁹⁰Y. ⁸⁹Sr and ⁹⁰Sr could be determined about 5 and 9 days after a nuclear explosion, respectively.     

Distribution of strontium in milk component

The distribution of strontium between the milk components, i.e., serum, casein micelles, whey and hydroxyapatite was determined. The sorption on hydroxyapatite was investigated using batch method and radiotracer technique. The aqueous phase comprised of either milk or whey. The sorption of strontium on hydroxyapatite depended on the method of its preparation and on the composition of the aqueous phase. The sorption of strontium was increased with an increase of pH. The presence of citrate species resulted in decrease of the sorption of strontium on hydroxyapatite. The sorption of ⁸⁵Sr on hydroxyapatite decreased with the increasing concentration of Ca²⁺ ions. Addition of Ca²⁺ ions to milk resulted in milk pH decrease. The decrease in pH value after calcium addition to milk is related to exchanges between added calcium and micellar H⁺. The average value of strontium sorption on casein micelles in milk with presence of hydroxyapatite was (47.3 ± 5.6) %. The average value of sorption of ⁸⁵Sr on casein micelles in milk without the addition of hydroxyapatite was (68.9 ± 2.2) %.