Extractive scintillating resin for 99Tc quantification in aqueous solutions

A method utilizing extractive scintillating resin for ⁹⁹Tcmonitoring in aqueous solutions is presented. These extractive scintillatorscombine analyte selective uptake and scintillating properties to produce dualfunctionality analytical resins. These resins were produced by (1) co-locatedextraction chromatographic resin and plastic scintillating beads, (2) immobilizingfluors in macroporous polystyrene supports to which chains of monomethylatedpolyethylene glycol have been grafted and (3) co-immobilizing organic scintillatingfluors and a quaternary ammonium extractant (Aliquat-336) within macroporousacrylic and polystyrene supports. The first and third resins selectively extractpertechnetate ions from dilute acid whereas the second resin selectively extractspertechnetate ions from high ionic strength solutions. These resins were utilizedin ~0.20 ml pore volume columns while ⁹⁹Tc was continually monitoredwith commercially available scintillation detection systems. Manual and automatedmicrofluidics were used to deliver sample and reagent solution for loadingand elution of the ⁹⁹Tc. The detection efficiencies were determinedto be 45 and 70% for acrylic and polystyrene based resins, respectively, andindependent of extractant. Minimum detectable ⁹⁹Tc concentrationusing the Aliquat-336/acrylic-based resin was 6.2 Bq . l –1 for a 50-mlsample and 30-minute count time. The new methodology was applied towards analysisof contaminated groundwater samples and nuclear waste simulants.     

Comparison of the TEVA-Spec resin and liquid-liquid extraction methods for the separation of technetium in soil samples

When ICP-MS is used for⁹⁹Tc measurements, elements which interfere with⁹⁹Tc counting should be removed. In this study, a separation method using a novel chromatographic resin (TEVA·Spec^® resin) was compared with a liquid-liquid extraction (LLX) method for separation and concentration of⁹⁹Tc which was trapped in a solution after combustion of environmental soil samples. The results showed that Tc could be separated from Ru at high recoveries with both separation methods. Molybdenum, however, was not removed by LLX, while more than 99% of Mo in soil samples were removed by TEVA·Spec resin.     

Determination of 99Tc in evaporator concentrates using solid phase extraction techniques

This paper describes a simple and rapid method of ⁹⁹Tc pre-concentration, separation and purification by using AnaLig^? Tc02 gel in two stages or AnaLig^? Tc02 gel in a first stage and TEVA^? resin in a second stage, which are commercially available from IBC advanced technologies, Inc. and Eichrom technologies, Inc., respectively. The method is suitable for analyzing large volume concentrate samples in a relatively short time. The use and effectiveness of AnaLig^? Tc02 and Eichrom’s TEVA^? resin were successfully tested by analysis of evaporator concentrate samples which belong to the class of most difficult matrices to analyze.     

Comparison of a radiation counting method and ICP-MS for the determination of99Tc in environmental samples

Results of⁹⁹Tc measurements between radiation and non-radiation counting methods were compared using four radiation sources for which⁹⁹Tc has been previously determined with a gas-flow proportional counter or a GM counter. Each⁹⁹Tc source consisted of a stainless steel planchet bound by mylar films. Seaweeds collected from the Irish Sea were analyzed and⁹⁹Tc was electroplated on the planchet. The⁹⁹Tc in each sample was separated and measured again by inductively coupled plasma mass spectrometry (ICP-MS). Tc was continuously removed from each sample with 2M HNO₃ and 2M NaOH. After the solution containing Tc was adjusted to 0.1M HNO₃, Tc was extracted on a novel extraction chromatographic resin to separate it from Ru. The total recoveries for Tc on the planchet samples were almost the same with an average of 91%. The results of⁹⁹Tc measurements by both radiation and non-radiation counting methods agreed well with each other.     

Cross-sections for formation of 99mTc through natRu(n,x) 99mTc reaction induced by neutrons at 13.5 and 14.8 MeV

The cross-sections for formation of metastable state of ⁹⁹Tc (^99mTc, 140.511 keV, 6.01 h) through ^natRu(n,x)^99mTc reaction induced by 13.5 MeV and 14.8 MeV neutrons were measured. Fast neutrons were produced via the ³H(d,n)⁴He reaction on the K-400 neutron generator. Induced gamma activities were measured by a high-resolution gamma-ray spectrometer with a high-purity germanium (HpGe) detector. Measurements were corrected for gamma-ray attenuations, dead time and fluctuation of neutron flux. Data for ^natRu(n,x)^99mTc reaction cross sections are reported to be 9.6±1.5 and 9.2±1.1 mb at 13.5±0.2 and 14.8±0.2 MeV incident neutron energies, respectively. Results were compared with the data by other anthors.     

Determination of technetium-99 in aqueous samples by isotope dilution inductively coupled plasma-mass spectrometry

An isotope dilution/inductively coupled plasma mass spectrometric method (ID/ICP-MS) for measuring the concentration of technetium-99 in aqueous samples was developed at the Savannah River Technology Center (SRTC). The procedure is faster than radiometric tecniques, is less subject to interferences, and has equal or better detection limits. It is currently being used to measure the concentration of⁹⁹Tc in samples of Savannah River water collected in the vicinity of the Savannah River Site. In this method one liter samples of water are spiked with⁹⁷Tc. After equilibration, the technetium is extracted from the sample with a chromatographic resin. Interfering elements, molybdenum and ruthenium, are either not retained by the resin or are washed off with, dilute nitric acid. The technetium is then eluted with more concentrated nitric acid, and the⁹⁹Tc/⁹⁷Tc ratio in the eluant is measured with an ICP-MS. The⁹⁹Tc concentration in the original sample is calculated from the⁹⁹Tc/⁹⁷Tc ratio. The chemical recovery of the extraction procedure is greater than 90%. The detection limit of the instrument, taken as three times the background counts atm/z=99, is 0.6 part per trillion (ppt). The detection limit of the procedure, taken as three times the standard deviation of several reagent blank analyses, is 0.33 pCi/l.     

Method for the detection of Tc in seaweed samples coupling the use of Re as a chemical tracer and isotope dilution inductively coupled plasma mass spectrometry

Analysis of the artificial radionuclide ⁹⁹Tc in environmental samples requires a chemical separation due to its low concentration, and therefore the use of a chemical yield tracer is peremptory. From a practical viewpoint, Re can be used for this purpose, due to its chemical similarities with Tc. Thus, the use of a radioactive tracer for Tc recovery calculation can be avoided. However, results from a recent intercomparison exercise showed that using of Re as a chemical yield tracer appears to underestimate the Tc concentration relative to the result obtained with isotopes of Tc. In the present work, the methodology used to design a simple separation method for the measurement of ⁹⁹Tc in environmental samples is described. Tc recovery is estimated throughout the Re recovery calculation by the isotope dilution technique coupled with ICP-MS (ID-ICP-MS) technique. For chemical separation, a chromatographic resin is used. Interfering elements are removed using a resin washing step carefully designed to avoid any element fractionation between Re and Tc; the care taken in this step is of major importance to assure the equivalence of the chemical recoveries for both elements. Agreement is tested using five replicates of five seaweed samples. The average recoveries for ^95mTc and Re were 93±6 and 95±7%, respectively, those are within the uncertainty intervals for each other. The results explained here demonstrate the possibility of applying Re chemical recoveries to calculate the Tc concentrations with the advantage of not introducing systematic errors.     

Determination and lebels of99Tc in environmental and biological samples

In this paper, the physical and chemical methods used in our laboratory for the measurement of⁹⁹Tc in natural samples are reviewed. Levels of⁹⁹Tc in rainwater, algae, and freshwater samples are given. In addition, and estimation of the radiological impact of⁹⁹Tc to the population, derived from our earliear atmospheric⁹⁹Tc measurements, is presented. For rainwater, levels of¹³⁷Cs are also given for comparison.Work partially supported by the contract PB86-0207 of the Spanish CICYT.     

Measurements of activation cross-sections for the 101Ru(n,p)101Tc reaction for neutrons with energies between 13 and 15 MeV

In this study, activation cross-sections were measured for the ¹⁰¹Ru(n,p)¹⁰¹Tc reaction at three different neutron energies from 13.5 to 14.8 MeV. The fast neutrons were produced via the ³H(d,n)⁴He reaction on K-400 neutron generator. Induced gamma activities were measured by a high-resolution gamma-ray spectrometer with high-purity germanium detector. Measurements were corrected for gamma-ray attenuations, random coincidence (pile-up), dead time and fluctuation of neutron flux. The data for ¹⁰¹Ru(n,p)¹⁰¹Tc reaction cross-sections are reported to be 15.7 ± 2.0, 18.4 ± 2.7 and 22.0 ± 2.4 mb at 13.5 ± 0.2, 14.1 ± 0.2, and 14.8 ± 0.2 MeV incident neutron energies, respectively. Results were compared with the previous works.     

Sorption and separation of some elements of nuclear importance using Chelex-100

Chelex-100, in the anionic form has been studied for its ability to perform selective separation and concentration of some metal ions of nuclear importance from mineral acid solutions. The sorption behavior of Zr(IV)–Nb(V), Mo(VI), Tc(VII), Te(IV) and U(VI) from solutions of hydrochloric and sulphuric acids on Chelex-100 has been studied under static and dynamic conditions. Mo(VI) and Tc(VII) have been concentrated on the resin from hydrochloric or sulphuric acid solutions at low acidities probably, as the anions MoO ₄ ^2– and TcO ₄ ^– , respectively. Te(IV) has been isolated from hydrochloric acid solutions of normalities 6 in the form of the anionic chloro complex TeCl ₆ ^2– . Optimum conditions for elution and separation of Mo(VI), Tc(VII), Te(IV) and U(VI) were recommended.     

Chemical and radiochemical evaluation of the purity of99mTc extracted by MEK

Solvent extraction separation of^99mTc from⁹⁹Mo using methyl ethyl ketone(MEK) has been found to be an effective method of obtaining^99mTc of medicinal purity from low specific activity⁹⁹Mo. The authors have investigated the effect of alkali and molybdenum concentration on the extraction of⁹⁹Mo and^99mTc into methyl ethyl ketone. The possibility of methyl ethyl ketone forming enol and condensation products and its effect on the final extraction efficiency and purity of^99mTc has been studied. Sodium molybdate has been found to have a good salting out effect on^99mTc pertechnetate and hence^99mTc extraction can be better accomplished from low specific activity⁹⁹Mo solutions. The ketone seems to form traces of condensation products in the extraction procedure. These have been found to be coextracted with^99mTc into MEK but did not affect the extractability of^99mTc. It was observed that neutral alumina column removes these condensation products from MEK containing^99mTc. Alternately these could be filtered off by acidification of the final aqueous^99mTc solution. The studies indicate that under optimum experimental conditions methyl ethyl ketone separates^99mTc from⁹⁹Mo with high efficiency and yields^99mTc of high purity suitable for use in nuclear medicine in the form of various labelled compounds.     

Study on the method of preparation <Superscript>97</Superscript>Tc

Technetium-99 is one of several long-lived fission products which, when detected in the environment can give an indication of a specific nuclear activity. The most sensitive analytical technique for ⁹⁹Tc yet reported is by isotopic dilution mass spectrometry with technetium-97 as the yield tracer. A method for the preparation of ⁹⁷Tc is reported in this paper. ⁹⁷Tc was obtained by irradiation of a sample of natural ruthenium metal in a high flux reactor. After cooling for 2 years, the technetium was isolated from the sample by technique combining; deposition, solvent extraction, and ion-exchange chromatography techniques. ^99mTc and ¹⁰³Ru were used as radio-tracers for the process. The results showed that more than 70% of the Tc was recovered the decontamination factor is more than 2.3 × 10⁷. The ⁹⁷Tc was calibrated by isotope dilution mass spectrometry with ⁹⁹Tc as the yield tracer. The final yield was 29.56 μg of ⁹⁷Tc suitable for use as a mass spectrometric spike (weight % ⁹⁷Tc spike: ⁹⁷Tc, 84.77%; ⁹⁸Tc, 15.03%; ⁹⁹Tc, 0.20%).     

Determination of low-level99Tc in environmental samples by high resolution ICP-MS

An analytical method has been developed for the determination of low-level⁹⁹Tc in environmental samples by High Resolution ICP-MS. The method consists of leaching of⁹⁹Tc by HNO₃ and separation by three different solvent extractions with 30% TOA-xylene, MEK, and cyclohexanone. Finally, purification of⁹⁹Tc was made by using an anion exchange resin column to reduce dissolved solids content. The final solution was adjusted to 1M HNO₃ for introducing into the HR-ICP-MS. The accuracy and precision of the method was confirmed to be satisfactory by applying this technique to the determination of⁹⁹Tc in IAEA marine algae sample (AG-B-1). Measurements of⁹⁹Tc using 0.5–2.5 g of sediment samples from the Irish Sea, UK, were successfully performed by the present method.     

Shedding Light on the Enigmatic TcO2 ⋅ xH2O Structure with Density Functional Theory and EXAFS Spectroscopy**

The β-emitting ⁹⁹Tc isotope is a high-yield fission product in ²³⁵U and ²³⁹Pu nuclear reactors, raising special concern in nuclear waste management due to its long half-life and the high mobility of pertechnetate (TcO₄⁻). Under the conditions of deep nuclear waste repositories, Tc is retained through biotic and abiotic reduction of TcO₄⁻ to compounds like amorphous TcO₂ ⋅ xH₂O precipitates. It is generally accepted that these precipitates have linear (Tc(μ-O)₂(H₂O)₂)_n chains, with trans H₂O. Although corresponding Tc−Tc and Tc−O distances have been obtained from extended X-ray absorption fine structure (EXAFS) spectroscopy, this structure is largely based on analogy with other compounds. Here, we combine density-functional theory with EXAFS measurements of fresh and aged samples to show that, instead, TcO₂ ⋅ xH₂O forms zigzag chains that undergo a slow aging process whereby they combine to form longer chains and, later, a tridimensional structure that might lead to a new TcO₂ polymorph.     

Rapid separation of VI/VII technetium oxidation states by solvent extraction with iodonitrotetrazolium chloride

Technetium⁹⁹ poses a difficult problem at many nuclear waste disposal sites, as there have been multiple incidents of its release to the environment due to large quantities of fission products disposed in storage tanks. Tc is mostly present under two oxidation states, Tc(VII) and Tc(IV) and the separation of Tc(IV) from Tc(VII) is often crucial for laboratory-scale work performed for the study of Tc. This work offers a method for the rapid separation of Tc(IV) from Tc(VII), using a solvent extraction system containing iodonitrotetrazolium chloride and chloroform.     

Reduction of Pertechnetate by Chemical and Photochemical Approaches and Incorporation of Tc(IV) into Titanium Dioxide

Technetium-99 is a prevalent fission product from nuclear waste. The long half-life (211,000 yr) and environmental mobility of pertechnetate (TcO₄⁻) render Tc particularly challenging to isolate and stabilize. Here we present two approaches for development of potential wasteforms using titanium dioxide, TiO₂. Approach 1 is a low temperature chemical synthesis of TiO₂ doped with Tc(IV) from TcO₄⁻ intended to mimic the Tc waste stream from the UREX family of separations and removes 98.5 % of the Tc, mainly present as edge-shared Tc(IV) pairs. Approach 2 utilizes TiO₂ to photocatalytically reduce TcO₄⁻ to Tc(IV) stabilized on the surface of or within the TiO₂ lattice. The %Tc removed from solution and adsorbed to TiO₂ is pH dependent, with the maximum Tc(IV) adsorbed at pH 3–4 as either TcO₂ or edge-sharing Tc(IV) octahedra. The Tc(IV)-TiO₂ composites materials formed by both approaches are suitable for consolidation into a dense wasteform by Hot Isostatic Pressing (HIPing).     

Separation and concentration of technetium using a Tc-selective extraction chromatographic resin

For⁹⁹Tc separation from environmental samples, liquid-liquid extraction, ion-exchange chromatography and coprecipitation, have been described. Although these methods are removing matrix elements, some combinations of them is necessary for purification and concentration of Tc. Besides, the procedures are time-consuming and generally a week or more is needed to purify Tc in the samples. In this study, a novel extraction chromatographic resin for the separation and preconcentration of Tc from several kinds of solutions is described. The material is shown to retain Tc efficiently and selectively from these solutions. Sorbed Tc is readily recovered using 5 ml of 12M HNO₃ and the recoveries with^95mTc are more than 97% for all sample solutions.     

Activation analysis for technetium-99 by the use of a neutron-excitation reaction

The formation of^99mTc was observed when⁹⁹Tc was irradiated by reactor neutrons as a result of the⁹⁹Tc(n, )^99mTc reaction. A good linearity was observed between the activities of^99mTc produced and⁹⁹Tc irradiated. The cross section of the excitation reaction was estimated to be 0.24 b. The application of the nuclear excitation reaction to the activation analysis for low level⁹⁹Tc was studied.     

Technetium-99m extraction and transport across tri-n-octylamine-xylene based supported liquid membranes

The nuclear properties of^99mTc radionuclide are ideal for organ imaging. Study of the technetium transport across supported liquid membranes has been performed to get data for its separation from other elements. Tri-n-octylamine diluted in xylene was used to constitute the liquid membranes, supported in polypropylene microporous films. Stripping on the product solution side was performed with dilute NaOH solutions. The effect of sulphuric acid, nitric acid and hydrochloric acid in the feed on transport of^99mTc as TcO ₄ ^– ions has been studied. The permeability of the given ions determined from kinetic activity data has been found to be in the order of PH₂SO₄>PHCl>PHNO₃. The flux values have been calculated based on this permeability data. The increase in carrier concentration has shown an increase in flux and permeability values to a given optimum concentration. The increase in temperature has been found to reduce the transport of Tc ions. The optimum conditions for transport of^99mTc for the given acid concentration have been determined. Mechanism of Tc ion transport has also been provided based on chemical reactions involved at the membrane interfaces and uptake of Tc ions by the membrane. MoO ₄ ^2– ions do not permeate through membrane under optimum conditions of transport for TcO ₄ ^2– ions from H₂SO₄ solution.     

Contributions to the coordination chemistry of technetium

The radionuclide^99mTc is widely used in nuclear medical diagnostics. Radiopharmaceuticals containing coordination compounds labeled with^99mTc⁴⁺ or^99mTc⁵⁺ can be rapidly prepared from pertechnetate eluted from a⁹⁹Mo/^99mTc generator. For the optimization of the imaging agent it is essential to determine the exact chemical structure of the Tc complex. This can be achieved by synthesizing macroscopic amounts of the analogous long-lived^99gTc compound and by its analysis by appropriate spectroscopy methods. We have successfully synthesized and characterized new technetium complexes with amino acids and also with ligands containing nitrogen, oxygen and sulfur atoms.