Feasibility study of an analytical method for detecting <Superscript>90</Superscript>Sr in soil using DGA resin and Sr resin

This study investigated an analytical method for detecting ⁹⁰Sr in soil samples for the routine monitoring of environmental radioactivity. Mineral acid leaching and fusion methods were first used to digest the soil sample, and the analytical results were compared. DGA resin was employed to separate ⁹⁰Y, being a daughter of ⁹⁰Sr. Then, ⁹⁰Y was analyzed by liquid scintillation counter (LSC). These analytical results were compared with those obtained using Sr resin, which is a well-known, simple and reliable separation method. With the DGA resin approach a minimum detectable activity of ~0.28 Bq kg^?1 was detected in a 50 g sample, with 180 min of counting time, 70% recovery and ~97% counting efficiency using a LSC.     

Preparation and quality control and biodistribution studies of [90Y]-DOTA-cetuximab for radioimmunotherapy

Yttrium-90 is a useful radionuclide for radioimmunotherapy (RIT) and the anti-epidermal growth factor receptor (anti-EGFR) antibody cetuximab is clinicsally approved for the treatment of EGFR-expressing metastatic colorectal cancer and advanced head and neck cancer. Thus in this work radiolabeling of monoclonal anti-EGFR with ⁹⁰Y for radioimmunotherapy (RIT) is targetted. Cetuximab was successively labeled with [⁹⁰Y] chloride (74 MBq) 2 mCi after conjugation with macrocyclics bifunctional chelating agent, 1,4,7,10-tetraazacyclododecane-N,N′,N″,N″′-tetraacetic acid mono-(N-hydroxysuccinimidyl) ester (DOTA-NHS), purified and concentrated by centrifugation using an Amicon Ultra-15 filter (Millipore, MWCo, 30000). ⁹⁰Y chloride was obtained by ⁹⁰Sr/⁹⁰Y generator. Radiolabeling was completed in 2 h by the addition of DOTA-cetuximab conjugate at 42 °C. The stability of radiolabeled was studied in human serum. Biodistribution studies in normal rats were carried out to determine the radioimmunoconjugate distribution up to 96 h. Radiochemical purity of 92 % (using ITLC) was obtained for final radioimmunoconjugate (Specific activity = 0.55 GBq/mg). Stability of radiolabeled protein in presence of human serum was tested at 37 °C for up to 24 h. Biodistribution studies demonstrated the highest ID/g % in the blood (2.62 ± 0.005 at 24 h) and the liver (2.19 ± 0.001). This study demonstrated that ⁹⁰Y-DOTA-cetuximab is a potential compound for the treatment of EGFR-expressing cancers.     

Separation of 90Y from 90Sr using sequential multiple column extraction chromatography

The distribution coefficient measurements on Y(III) and Sr(II) were performed using ditertiarybutyl dicyclohexano 18-crown-6 (Sr-selective resin) and N,N,N′,N′-tetraoctyldiglycolamide (Y-selective resin) in HNO₃, HCl and HClO₄ media. Separation factors (⁹⁰Y/⁹⁰Sr) based on distribution coefficient data suggested that perchloric acid is distinctly better medium as compared to nitric acid/hydrochloric acid. The mechanism of extraction changes with the nature and concentration of acid and is responsible for the high selectivity in perchloric acid medium. Sequential column studies were carried out on tracers (radioactive/stable) employing Sr-selective/Y-selective extraction chromatographic resins as stationary phases. The final elution of ⁹⁰Y was done in 0.01 M EDTA at pH 4.0 which can be used for clinical applications after radiochemical processing.     

Determination of 90Sr in Portuguese foodstuffs

The Nuclear and Technological Institute (ITN) has the legal responsibility to carry out the environmental radiological monitoring at a national level. This survey was planned to provide relevant information on radioactivity levels in different components of the ecosystem. In what concerns the terrestrial environment the evaluation of the ⁹⁰Sr activity concentrations in foodstuffs has been performed using a method based on the separation of ⁹⁰Sr by extraction chromatography and beta determination by liquid scintillation counting (LSC) technique. The trials were carried out using 7 g of ash samples and 3 g of commercial Sr-resin (Eichrom). Validation trials were also performed using ⁹⁰Sr spiked samples. The chemical yields were determined by gravimetric method, after the addition of stable strontium to the foodstuffs. The ⁹⁰Sr activity concentrations in complete meals, meat and vegetables were determined after ⁹⁰Y ingrowths in the region 12–862 keV, using the Tri-Carb 3170 TR/SL scintillation counter in normal mode and a counting time of 120 min. The results obtained were low and of the same order of magnitude of those reported by other European countries.     

Modified 2-window approach for rapid determination of 90Sr and 90Y at low quench level using liquid scintillation counting

⁹⁰Sr is a product of nuclear fission, the radioactivity of which can be determined by liquid scintillation counting (LSC). Because the LSC spectra of ⁹⁰Sr and its daughter ⁹⁰Y overlap each other, the following methods are usually used: (1) measuring immediately after ⁹⁰Sr/⁹⁰Y separation; (2) waiting to reach radioactive equilibrium; (3) adopting the conventional 2-window approach; and (4) using the spectra deconvolution technique. The first one requires ⁹⁰Sr/⁹⁰Y separation and immediate measurement; the second one is time-consuming; the third one is valid only for samples with the same quench level as the calibration standard; the last one is somewhat complicated, and in some cases it is not convenient to export the experimental data to some deconvolution software. Therefore, we have developed a modified 2-window approach to rapidly determine ⁹⁰Sr and ⁹⁰Y in either equilibrium or disequilibrium at low quench level. The key modification of the approach is to provide an LSC spectrum of pure ⁹⁰Y with the same quench level as the sample to be determined. This modification eliminates the need to conduct ⁹⁰Sr/⁹⁰Y separation for the sample itself, to prepare the quench curves, and to fit the LSC spectra with some deconvolution software.     

Separation of carrier-free 90Y from 90Sr using flat sheet supported liquid membranes containing multiple diglycolamide-functionalized calix[4]arenes

Abstract

Five diglycolamide-appended calix[4]arene (C4DGA) ligands, viz. C4DGA with no substituent (L-I), n-propyl (L-II), 3-pentyl (L-III), n-octyl (L-IV) and both side (L-V) substituents were evaluated for the separation of carrier free ⁹⁰Y from a ⁹⁰Y–⁹⁰Sr mixture using the flat sheet supported liquid membrane technique. Based on the results of earlier batch studies, the transport properties of the C4DGA ligands towards Y(III) and Sr(II) were monitored at two different feed acidities. The transport rates were significantly lower for 6 M HNO₃ as compared to 3 M HNO₃ as the feed. After 6 h, the observed trend of Y(III) transport with the C4DGA ligands using a feed of 3 M HNO₃ was: L-I ~ L-III > L-V > L-IV > L-II which changed to L-III > L-I > L-IV > L-V > L-II for 6 M HNO₃ as the feed. With 3 M HNO₃ as feed, >97% Y(III) transport was obtained with L-I and L-III in 6 h. Comparative Sr(II) transport was negligible resulting in high decontamination factors. In a one-step separation process, using L-I as the carrier ligand, pure ⁹⁰Y was obtained as the respective complex with either EDTA or DOTA. The highlights of this liquid membrane-based separation method comprise: its easiness, one-step separation, low ligand inventory, relatively pure product and continuous method.     

A rapid method for the determination of strontium-90 in powdered milk

A method in which⁹⁰Y the daughter product of⁹⁰Sr decay is extracted by tributyl phosphate (TBP) from ashed powdered milk is described. The⁹⁰Y which is in equilibrium with⁹⁰Sr is back-extracted into the aqueous phase and coprecipitated with milligram amounts of ferric hydroxide. The proposed procedure makes it possible to obtain thin planar sources convenient for low level gas counters. The overall detection efficiency of 45.5% for⁹⁰Y (including chemical recovery of yttrium) was achieved. The detection limit for 200 g powdered milk samples and 10 000 s counting time was 0.065 Bq·kg^–1. The concentration of⁹⁰Sr in three-year old samples (after Chernobyl accident) ranged from 0.81 to 1.31 Bq·kg^–1.     

Separation of Y from Sr by zirconium vanadate gel ion-exchanger sorbent: kinetics and thermodynamic study

A new zirconium vanadate (Zr–V) ion-exchanger was synthesized and characterized for fast and selective separation procedure of ⁹⁰Y from ⁸⁹Sr. The method was based on ⁹⁰Y(III) sorption from aqueous HCl solution containing ⁸⁹Sr(II) onto Zr–V gel exchanger. The kinetics of Y(III) sorption from HCl solution by Zr–V exchanger was subjected to Weber–Morris, Lagergren, Bhattacharya and Venkobachar, and Bt models. Initially, the uptake of Y(III) onto the exchanger was fast followed by kinetically first-order sorption with an overall rate constant, K _Lager = (3.55 ± 0.03) × 10^?4 min^?1. Film and intraparticle transport are the two steps that might influence Y(III) sorption. The negative values of ΔG of ⁹⁰Y retention dictate that, the process is a spontaneous. The negative values of ΔH and ΔS reflect the exothermic nature of ⁹⁰Y(IIsorption and the random uptake of ⁹⁰Y(III) onto Zr–V sorbent. Zr–V exchanger offers unique advantages of ⁹⁰Y(III) retention over conventional solid sorbents in rapid and effective separation of traces of ⁹⁰Y(III) from Sr. The exchanger was successfully packed in column for an effective separation of ⁹⁰Y.     

Studies on the separation of 90Y from 90Sr by solvent extraction and supported liquid membrane using TODGA: role of organic diluent

Solvent extraction and supported liquid membrane transport studies on Y(III) and Sr(II) were carried out using both nitric as well as hydrochloric acid feed conditions using N,N,N′,N′-tetra-octyldiglycolamide (TODGA) in several organic diluents. The solvent extraction studies indicated extremely large separation factor (SF) values with chloroform, carbon tetrachloride, 1-decanol and hexone when 6 M HNO₃ was used as the feed. On the other hand, the SF values were 1–2 orders of magnitude lower when the nitric acid concentration was 3 M HNO₃. Significantly large SF values were also obtained from 6 M HCl when xylene, carbon tetrachloride, n-dodecane and hexone were used as the diluent. Though mass transfer was not very promising in the supported liquid membrane studies with most of the diluent systems, quantitative Y(III) transport was observed with 0.1 M TODGA in xylene with negligible Sr(II) transport suggesting possibility of obtaining carrier free ⁹⁰Y. The purity of the radiotracer was checked by half-life method.     

Rapid determination of radiostrontium in seawater samples

A new method for the determination of radiostrontium in seawater samples has been developed at the Savannah River National Laboratory (SRNL) that allows rapid pre-concentration and separation of strontium and yttrium isotopes in seawater samples for measurement. The new SRNL method employs a novel and effective pre-concentration step that utilizes a blend of calcium phosphate with iron hydroxide to collect both strontium and yttrium rapidly from the seawater matrix with enhanced chemical yields. The pre-concentration steps, in combination with rapid Sr Resin and DGA Resin cartridge separation options using vacuum box technology, allow seawater samples up to 10 L to be analyzed. The total ⁸⁹Sr + ⁹⁰Sr activity may be determined by gas flow proportional counting and recounted after ingrowth of ⁹⁰Y to differentiate ⁸⁹Sr from ⁹⁰Sr. Gas flow proportional counting provides a lower method detection limit than liquid scintillation or Cerenkov counting and allows simultaneous counting of samples. Simultaneous counting allows for longer count times and lower method detection limits without handling very large aliquots of seawater. Seawater samples up to 6 L may be analyzed using Sr Resin for ⁸⁹Sr and ⁹⁰Sr with a minimum detectable activity (MDA) of 1–10 mBq/L, depending on count times. Seawater samples up to 10 L may be analyzed for ⁹⁰Sr using a DGA Resin method via collection and purification of ⁹⁰Y only. If ⁸⁹Sr and other fission products are present, then ⁹¹Y (beta energy 1.55 MeV, 58.5 day half-life) is also likely to be present. ⁹¹Y interferes with attempts to collect ⁹⁰Y directly from the seawater sample without initial purification of Sr isotopes first and ⁹⁰Y ingrowth. The DGA Resin option can be used to determine ⁹⁰Sr, and if ⁹¹Y is also present, an ingrowth option with using DGA Resin again to collect ⁹⁰Y can be performed. An MDA for ⁹⁰Sr of <1 mBq/L for an 8 h count may be obtained using 10 L seawater sample aliquots.     

Determination of 90Sr and 210Pb in freshwater fish in Austria

A method for the determination of ⁹⁰Sr and ²¹⁰Pb in freshwater fish was developed. The determinations were conducted within a project on behalf of the Federal Ministry of Health. The aim of this project was to get an overview of the activity concentrations of natural and artificial radionuclides in freshwater fish in different lakes in Austria. For sampling the Neusiedler See in Burgenland, two lakes in Styria the Grundlsee and the Toplitz See, and the Zeller See in Salzburg were chosen. Chub (Leuciscus cephalus), pike (Esox lucius), perch (Perca fluviatilis), carp (Cyprinus carpio), catfish (Silurus glanis), pike-perch (Sander lucioperca) and burbot (Lota lota) were analysed. The samples were analysed using strontium specific extraction columns (Eichrom Industries Inc., TrisKem International) and liquid scintillation counting. In the edible parts of the fish samples (no fishbone) values of the activity concentration for ²¹⁰Pb varied between 0.009 ± 0.003 and 0.16 ± 0.04 Bq kg _freshweight ^?1 and for ⁹⁰Sr between 0.010 ± 0.002 and 0.11 ± 0.02 Bq kg _freshweight ^?1 . In this paper the method for the determination of ⁹⁰Sr and ²¹⁰Pb is described and the results are discussed.     

Recovery and purification of Sr(II) in perchloric acid medium

Perchloric acid was found to be a suitable medium for the quantitative leaching of Sr(II) from homogeneous and calcined (Th,Sr)O₂ particularly with respect to the contamination from Th(IV). ⁹⁰Sr is a cause of major concern to the environment due to its long half life (28.6 years), significant abundance in large inventory of spent nuclear fuels (~350 thousand tons) awaiting geological disposal and its chemical similarity to Ca(II), an essential element for the living beings. Application of ⁹⁰Sr as a parent radionuclide for ⁹⁰Y (used in therapy radiopharmaceuticals) is possible provided it can be made available at desired high purity. In this context, the distribution coefficients of Sr(II), Th(IV), Zr(IV), Y(III), ¹⁵²Eu(III) and ¹³⁷Cs(I) were determined using Sr selective crown ether 4,4′(5′)-di-tert-butyl-dicyclohexano-18-crown-6 by solid–liquid extraction in perchloric acid medium. Feasibility of employing extraction chromatography using Sr selective resin for the recovery and purification of Sr(II) from leached perchloric acid medium was explored. Perchloric acid medium is better than nitric acid medium for the uptake of Sr by Sr selective chromatographic resin under varying loading conditions of Sr(II). Similarly pH 2 solution appears better eluent of Sr(II) than distilled water. Present work offers a novel approach for setting up a ⁹⁰Sr–⁹⁰Y generator.     

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.     

A rapid method for determining strontium-90 in urine samples

Rapid bioassay methods for ⁹⁰Sr in urine samples are needed to provide an early estimation of possible internal dose resulting from exposure to radiostrontium in the event of a radiological and nuclear emergency. In this work, a fast column separation method followed by liquid scintillation counting for detection of ⁹⁰Sr in urine was developed. Replicate spike and blank samples were analyzed for performance evaluation of the method. Using this method, a detection limit of ~10 Bq L^?1 for ⁹⁰Sr can be achieved with a sample analysis turn-around time of 4 h for a set of 12 samples. The method is adequate to meet the radiobioassay acceptance criteria and is suitable for quick dose assessment of ⁹⁰Sr exposure following a radiation emergency.     

Atmospheric depositional fluxes of cosmogenic <Superscript>32</Superscript>P, <Superscript>33</Superscript>P and <Superscript>7</Superscript>Be in the Sevastopol region

⁹⁰Y was separated from ⁹⁰Sr using an extraction chromatographic resin consisting of 4, 4′(5′)-bis-t-butylcyclohexano-18-crown-6 (DtBuCH₁₈C₆), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) amide (C₂mimNTf₂), and a polymer (Amberlite XAD-7). Ionic liquid was introduced into the column to improve the separation efficiency. The column showed an excellent performance for the separation of Y from Sr. After the separation, the ratio of ⁹⁰Sr/⁹⁰Y was <2.0 × 10^?5; the column was recycled for >18 times. This study provides preliminary results on columns to produce ⁹⁰Y with a high purity in radiopharmaceuticals.     

Rapid determination of 90Sr/90Y in water samples by liquid scintillation and Cherenkov counting

Strontium-90 (⁹⁰Sr) is a ubiquitous contaminant at nuclear facilities, found at high concentrations in spent nuclear fuel and radioactive waste. Due to its long half-life and ability to be transported in groundwater, an accurate method for measuring ⁹⁰Sr in water samples is critical to the monitoring program of any nuclear facility. To address this need, a rapid procedure for sequential separation of Sr/Y was developed and tested in groundwater samples collected from an area of riverbed affected by a ⁹⁰Sr groundwater plume. Sixteen samples, plus spike and water blanks, were analyzed. Five different measurements were performed to determine the ⁹⁰Sr and yttrium-90 (⁹⁰Y) activities in the samples: direct triple-to-double-coincidence ratio (TDCR) Cherenkov counting of ⁹⁰Y, liquid scintillation (LS) counting for ⁹⁰Sr following radiochemical separation, LS counting for ⁹⁰Y following radiochemical separation, Cherenkov counting for ⁹⁰Y following radiochemical separation and LS counting of the Sr samples for ⁹⁰Y in-growth. The counting was done using a low-level Hidex 300SL TDCR counter. Each measurement method was compared for accuracy, sensitivity and efficiency. The results following Cherenkov counting and radiochemical separation were in very good agreement with one another.     

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.     

The use of liquid scintillation spectrometry for the determination of radionuclidic purity of 90Y from a radiochemical 90Y/90Srgenerator

Summary An extraction technique for the separation of ⁹⁰Sr from a high excess of⁹⁰Y has been developed. This procedure can be used for the determination of trace amounts of⁹⁰Sr in⁹⁰Y prepared by a radiochemical⁹⁰Y/⁹⁰Sr generator by liquid scintillation.     

A prototype of an extrapolation chamber for beta radiation beams of 90Sr+90Y

Extrapolation chamber is the only primary standard dosimeter for beta radiation. With the aim to test new configurations and materials using easily-available and low-cost materials and fulfill the need of a chamber for scientific metrological purposes, in this paper the prototype of an extrapolation chamber has been built and its performance has been investigated in the beta radiation field of ⁹⁰Sr+⁹⁰Y. The main differences between the chamber and commercially available chambers are the geometry, constituent material and configuration. The obtained results were compared with those of the calibration certificate of the source and an agreement within 4 % was verified. The depth-dose curve was also obtained and compared with the curve published in ISO 6980, showing a good agreement. Moreover, Monte Carlo simulation was undertaken using MCNP4C code and the relative difference of 0.3 % was observed compared to the experiment. All of the results proved the suitability of the chamber in the beta radiation field of ⁹⁰Sr+⁹⁰Y.     

Validation of an extraction paper chromatography (EPC) technique for estimation of trace levels of 90Sr in 90Y solutions obtained from 90Sr/90Y generator systems

While the extraction paper chromatography (EPC) technique constitutes a novel paradigm for the determination of few Becquerels of ⁹⁰Sr in MBq quantities of ⁹⁰Y obtained from ⁹⁰Sr/⁹⁰Y generator, validation of the technique is essential to ensure its usefulness as a real time analytical tool. With a view to explore the relevance and applicability of EPC technique as a real time quality control (QC) technique for the routine estimation of ⁹⁰Sr content in generator produced ⁹⁰Y, a systematic validation study was carried out diligently not only to establish its worthiness but also to broaden its horizon. The ability of the EPC technique to separate trace amounts of Sr²⁺ in the presence of large amounts of Y³⁺ was verified. The specificity of the technique for Y³⁺ was demonstrated with ⁹⁰Y obtained by neutron irradiation. The method was validated under real experimental conditions and compared with a QC method described in US Pharmacopeia for detection of ⁹⁰Sr levels in ⁹⁰Y radiopharmaceuticals.