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.     

Alternate method of source preparation for alpha spectrometry: no electrodeposition,no hydrofluoric acid

Journal of Radioanalytical and Nuclear Chemistry - An alternate method of preparing actinide alpha counting sources was developed in place of electrodeposition or lanthanide fluoride...     

Optimization and characterization of a sulfate based electrodeposition method for alpha-spectroscopy of actinide elements using chemometric analysis

Alpha-spectrometric measurements using Si detectors is the standard method for the determination of alpha emitting actinide elements. This method requires the preparation of sources for analysis which do not degrade the energy spectrum of the emitted alpha particles via sample self-absorption. A variety of methods for the electrodeposition of actinides have been reported in the literature, many of which require long deposition times and lack reproducibility. A sulfate based method has been evaluated for the preparation of these sources using chemometric analysis to optimize the method and evaluate several variables and their interactions with the goal to achieve high yield source preparation in 1 hour or less. Typical resolution for this method is 30 keV or less with recoveries approaching unity.     

Evaluation of measurement uncertainty in the determination of 210Pb and 210Po using beta counting and alpha spectrometry

 Measurement uncertainties in the determination of ²¹⁰Pb and ²¹⁰Po in Reference Material IAEA-300 (Baltic Sea Sediment) were evaluated. ²¹⁰Pb and ²¹⁰Po were separated from the matrix using an Sr resin column. The chemical yield of ²¹⁰Pb was determined gravimetrically in PbSO₄ form. Precipitation was followed by beta proportional counting after ²¹⁰Bi ingrowth. ²¹⁰Po was determined by alpha spectrometry after its spontaneous deposition on a Cu planchet. The major source of uncertainty was identified as the statistical counting uncertainty, which was also expected and is almost impossible to reduce without extension of the time required for an analysis. The expanded uncertainties were determined as 7.4% and 12.2% for ²¹⁰Pb and ²¹⁰Po, respectively. Received: 3 September 2002 Accepted: 3 December 2002 Acknowledgement This work was financially supported by Ministry of Education, Science and Sport, Republic of Slovenia (Project group PO-0106–0532). Presented at CERMM-3, Central European Reference Materials and Measurements Conference: The function of reference materials in the measurement process, May 30–June 1, 2002, Rogaška Slatina, Slovenia Correspondence to P. Vreˇcek     

Ion chromatography inductively coupled plasma mass spectrometry (IC-ICP-MS) and radiometric techniques for the determination of actinides in aqueous leachate solutions from uranium oxide

The choice of the analytical method for the determination of actinide isotopes in leachate solutions has to be made considering several parameters: detection limit for each isotope, sample preparation procedure in terms of duration and complexity, counting time and interferences. A leachate solution obtained by keeping a pellet of UO₂ doped with ²³⁸Pu in contact with distilled water was investigated for the content of U and Pu isotopes by radiometric methods (α-, γ-spectrometry and liquid scintillation counting). The results of the radiometric methods were compared with those obtained from the analysis performed by inductively coupled plasma mass spectrometry on-line to a system for chromatographic separation (IC-ICP-MS). The comparison confirmed that IC-ICP-MS is a powerful method for the detection of long-lived radionuclides. The radiometric methods have a detection limit two orders of magnitude lower than IC-ICP-MS in the case of short-lived radioisotopes mostly due to the low background in the detector. On the other hand, the sample preparation and the analysis duration are more time-consuming compared to IC-ICP-MS; moreover, not all isotopes can be determined by using only one radiometric technique.     

A scintillation method for determination of actinide alpha-activity in samples

This report describes an efficient, easy to use, and inexpensive method for detection of alpha-activity in biological samples, the alpha radiometer. The actinide elements are coprecipitated from acid-dissolved, ashed samples with bismuth phosphate and the precipitate is then mixed with ZnS(Ag) scintillation powder. The mixture is dried, in a thin layer, on the surface of a polystyrene cuvet and scintillations from the layer are detected with a photomultiplier tube. An optimal counting efficiency is obtained with a scintillation powder thickness between 25 and 40 mg·cm⁻².     

Preparation of actinide targets for the synthesis of the heaviest elements

The heaviest elements are synthesized in heavy-ion induced hot fusion reactions with various actinide targets. Because the actinide material is often available only in very limited amounts, a deposition method with high yields (~90 %) is needed. We report on the production of ²⁴⁴Pu, ²⁴³Am, ²⁴⁸Cm, ²⁴⁹Bk, and ²⁴⁹Cf targets on thin Ti backings by molecular plating. Different chemical purification steps using ion chromatographic techniques were applied for the purification of ²⁴⁹Cf and ²⁴⁴Pu. The deposition procedure applied for the production of ~0.4–0.8 mg/cm² thick targets is described. The deposition yield was determined either by α-particle or γ-ray spectroscopy. Furthermore, neutron activation analysis has been applied in the case of ²⁴⁴Pu, ²⁴³Am, and ²⁴⁸Cm. Information about the spatial distribution and homogeneity of the target layer was obtained by radiographic imaging.     

Rapid separation of actinides and radiostrontium in vegetation samples

A new rapid method for the determination of actinides and radiostrontium in vegetation samples has been developed at the Savannah River Site Environmental Lab (Aiken, SC, USA) that can be used in emergency response situations or for routine analysis. The actinides in vegetation method utilizes a rapid sodium hydroxide fusion method, a lanthanum fluoride matrix removal step, and a streamlined column separation process with stacked TEVA, TRU and DGA Resin cartridges. Lanthanum was separated rapidly and effectively from Am and Cm on DGA Resin. Alpha emitters are prepared using rare earth microprecipitation for counting by alpha spectrometry. The purified ⁹⁰Sr fractions are mounted directly on planchets and counted by gas flow proportional counting. The method showed high chemical recoveries and effective removal of interferences. The actinide and ⁹⁰Sr in vegetation sample analysis can be performed in less than 8 h with excellent quality for emergency samples. The rapid fusion technique is a rugged sample digestion method that ensures that any refractory actinide particles or vegetation residue after furnace heating is effectively digested.     

An efficient quantitative technique for the simultaneous analyses of radon daughters (210)Pb, (210)Bi and (210)Po

An improved and time efficient technique has been developed for quantitative determination of the long-lived (222)Rn daughters ((210)Pb, (210)Po and (210)Bi) in atmospheric and oceanic samples. The sample is first spiked with yield tracers for polonium (208 or 209), bismuth (207), and lead (stable lead carrier). These nuclides may then be scavenged through iron hydroxide precipitation and redissolved in a dilute (pH approximately 2) nitric acid plating medium with citrate and hydroxylamine hydrochloride at 90 degrees centrigrade with constant stirring. First a silver planchet is suspended in the solution which plates polonium to high efficiency. Second, a nickel planchet is suspended in the same solution which is maintained hermetic (e.g. bubbling with helium) and bismuth is plated next with high efficiency. Third, lead is purified from the same solution using anion exchange techniques and isolated for beta counting as the sulfate. Polonium is analyzed by isotope dilution alpha spectrometry. Bismuth and lead are analyzed by anti-coincident beta counting in a low level shield. In the case of bismuth, the 207 tracer is added in quantities at least comparable to the background of the beta system such that counting before and after the decay of (210)Bi gives the bismuth yield. The unique characteristics of this technique are its speed and efficiency; all three radon daughters can be isolated for counting within 4 hr of pre-treating the sample. The remaining solution can be treated subsequently for other analyses as appropriate.     

Determination of long-lived fission products and actinides in Savannah River Site HLW sludge and glass for waste acceptance

Savannah River Site (SRS) is immobilizing the radioactive, high-level waste sludge in Tank 51 into a borosilicate glass for disposal in a geologic repository. A requirement for repository aceeptance is that SRS report the concentrations of certain fission product and actinide radionuclides in the glass. This paper presents measurements of many of these concentrations in both Tank 51 sludge and the final glass. The radionuclides were measured by inductively coupled plasma mass spectrometry and α, β, and γ counting methods. Examples of the radionuclides are⁹⁰Sr,¹³⁷Cs,²³⁸U and,²³⁹Pu. Concentrations in the glass are 3.1 times lower due to dilution of the sludge with a nonradio-active glass forming frit in the vitrification process. Results also indicated that in both the sludge and glass the relative concentrations of the long lived fission products insoluble in caustic are in proportion to their yields from the fission of²³⁵U waste in the SRS reactors. This allowed the calculation of a fission yield scaling factor. This factor in addition to the sludge dilution factor can be used to estimate concentrations of waste acceptance radionuclides that cannot be measured in the glass. Examples of these radionuclides are⁷⁹Se,⁹³Zr, and¹⁰⁷Pd.     

Alpha-beta discrimination liquid scintillation counting for uranium and its daughters

Advances in liquid scintillation counting (LSC) technologies, such as imporved scintillation cocktail formulations and alpha-beta radiation discrimination, make LSC suitable for applications in uranium process chemistry. Ease of use, low cost, and the huge dynamic range of LSC are distinct advantages for analytical support of actinide processing. All uranium isotopes decay primarily with alpha radiation emission. The immediate short-lived daughters of²³⁸U are²³⁴Th and²³⁴Pa. These nuclides are beta emitters having energy bands that overlap the uranium bands in a liquid scintillation spectrum. The resolution of these overlapping bands by alpha-beta radiation discrimination is useful for uranium quantification and purity verification. Protactinium-234 is a high-energy beta emitter that can be further identified and quantified from it's Cherenkov radiation. Energy spectra were collected on the Packard 2500AB liquid scintillator analyzer for uranyl solutions in diisopropylnaphthalene and pseudocumene based scintillator cocktails. Calibration curves were prepared for nitric, hydrochloric, and sulfuric acid media. Base titrations demonstrated the effect of acid quenching on those system. Ion exchange and water soluble polymer extraction studies are readily followed using liquid scintillation methods.     

Assessment of 210Po deposition in moss species and soil around coal-fired power plant

In the present study, the depositions of ²¹⁰Po were assessed in the surface soil and some mosses species found in the area around coal fired power plant using radiochemical deposition and alpha spectrometry counting system. The purposes of the study were to determine activity concentrations of ²¹⁰Po in mosses and surface soil collected around coal-fired power plant in relation to trace the potential source of ²¹⁰Po and to identify most suitable moss species as a bio-indicator for ²¹⁰Po deposition. In this study, different species of mosses, Orthodontium imfractum, Campylopus serratus and Leucobryum aduncum were collected in May 2011 at the area around 15 km radius from Tanjung Bin coal-fired power plant located in Pontian, Johor. The ²¹⁰Po activity concentrations in mosses and soil varied in the range 102 ± 4 to 174 ± 8 Bq/kg dry wt. and 37 ± 2 to 184 ± 8 Bq/kg dry wt., respectively. Corresponding highest activity concentration of ²¹⁰Po observed in L. aduncum, therefore, this finding can be concluded this species was the most suitable as a bio-indicator for ²¹⁰Po deposition. On the other hand, it is clear the accumulation of ²¹⁰Po in mosses might be supplied from various sources of atmospheric deposition such as coal-fired power plant operation, industrial, plantation, agriculture and fertilizer activities, burned fuel fossil and forest; and other potential sources. Meanwhile, the main source of ²¹⁰Po in surface soil is supplied from the in situ deposition of radon decay and its daughters in the soil itself.     

Rapid method for alpha counting with extractive scintillator and pulse shape analysis

A rapid method for alpha counting with liquid scintillation is presented. The interference of beta and gamma radiation with the determination of alpha emitting nuclides by liquid scintillation counting was examined. In extractive scintillator cocktail, TOPO-PPO-naphthalene-toluene has been developed for transferring actinide elements into organic scintillator and separating the undesirable materials as well as most beta emitters. Pulse Shape Analysis (PSA) was applied for the discrimination of beta radiation. The influence of cocktail composition on PSA has been studied and compared with that of the commercial cocktail. An analytical procedure was suggested for the rapid determination of actinide elements U, Pu, Am and Cm in the nuclear fuel cycle or in environmental samples.     

Ion chromatography inductively coupled plasma mass spectrometry (IC-ICP-MS) and radiometric techniques for the determination of actinides in aqueous leachate solutions from uranium oxide

The choice of the analytical method for the determination of actinide isotopes in leachate solutions has to be made considering several parameters: detection limit for each isotope, sample preparation procedure in terms of duration and complexity, counting time and interferences. A leachate solution obtained by keeping a pellet of UO2 doped with 238Pu in contact with distilled water was investigated for the content of U and Pu isotopes by radiometric methods (alpha-, gamma-spectrometry and liquid scintillation counting). The results of the radiometric methods were compared with those obtained from the analysis performed by inductively coupled plasma mass spectrometry on-line to a system for chromatographic separation (IC-ICP-MS). The comparison confirmed that IC-ICP-MS is a powerful method for the detection of long-lived radionuclides. The radiometric methods have a detection limit two orders of magnitude lower than IC-ICP-MS in the case of short-lived radioisotopes mostly due to the low background in the detector. On the other hand, the sample preparation and the analysis duration are more time-consuming compared to IC-ICP-MS; moreover, not all isotopes can be determined by using only one radiometric technique.     

Rapid determination of 210Po in water samples

A new rapid method for the determination of ²¹⁰Po in water samples has been developed at the Savannah River National Laboratory (SRNL) that can be used for emergency response or routine water analyses. If a radiological dispersive device event or a radiological attack associated with drinking water supplies occurs, there will be an urgent need for rapid analyses of water samples, including drinking water, ground water and other water effluents. Current analytical methods for the assay of ²¹⁰Po in water samples have typically involved spontaneous auto-deposition of ²¹⁰Po onto silver or other metal disks followed by counting by alpha spectrometry. The auto-deposition times range from 90 min to 24 h or more, at times with yields that may be less than desirable. If sample interferences are present, decreased yields and degraded alpha spectrums can occur due to unpredictable thickening in the deposited layer. Separation methods have focused on the use of Sr Resin?, often in combination with ²¹⁰Pb analysis. A new rapid method for ²¹⁰Po in water samples has been developed at the SRNL that utilizes a rapid calcium phosphate co-precipitation method, separation using DGA Resin^® (N,N,N′,N′ tetraoctyldiglycolamide extractant-coated resin, Eichrom Technologies or Triskem-International), followed by rapid microprecipitation of ²¹⁰Po using bismuth phosphate for counting by alpha spectrometry. This new method can be performed quickly with excellent removal of interferences, high chemical yields and very good alpha peak resolution, eliminating any potential problems with the alpha source preparation for emergency or routine samples. A rapid sequential separation method to separate ²¹⁰Po and actinide isotopes was also developed. This new approach, rapid separation with DGA resin plus microprecipitation for alpha source preparation, is a significant advance in radiochemistry for the rapid determination of ²¹⁰Po.     

Electrochemically modulated separations for rapid and sensitive isotopic analysis

The desire for more rapid and sensitive analytical determinations of actinides in the environment is being addressed in our laboratory through the development of electrochemically modulated separations (EMS) coupled to multiple ion counting inductively coupled plasma mass spectrometry (MIC-ICP-MS). This work is focused on the characterization of EMS separations of U and Pu in swipe materials. EMS provides electrochemically controlled surface complexation of either U(IV) or Pu(IV), depending on the potential applied to an anodized glassy carbon electrode. The accumulation and rinse yields ~90 % recovery efficiency, matrix elimination, and analyte concentration of the selected actinide. All this is performed solely under the control of the applied potential. Once isolated, the concentrated actinide is released into a ~1 μL volume of dilute (0.5 M) HNO₃, resulting in a volumetrically concentrated transient signal that is ideal for multiple ion counting detection. Coupled with a Thermo Fisher Scientific Neptune Plus MIC-ICP-MS, atom utilization efficiencies are normally 1 %, comparable to the gold standard thermal ionization mass spectrometry (TIMS), but only requiring 20 min for separation and analysis; whereas TIMS requires >50 h for off-line separation, filament preparation, and isotopic analysis. Method and analytical figures of merit will be highlighted.     

Determining the activity of <Superscript>241</Superscript>Pu by liquid scintillation counting

Liquid scintillation counting (LSC) is one of the most widely used methods for determining the activity of ²⁴¹Pu. One of the main challenges of this counting method is the efficiency calibration of the system for the low beta energies of ²⁴¹Pu (E _max = 20.8 keV). In this paper we compare the two most frequently used methods, the CIEMAT/NIST efficiency tracing (CNET) method and the experimental quench correction curve method. Both methods proved to be reliable, and agree within their uncertainties, for the expected quenching conditions of the sources.     

Soil and sediment sample analysis for the sequential determination of natural and anthropogenic radionuclides

A new sequential method for the determination of both natural (U, Th) and anthropogenic (Sr, Cs, Pu, Am) radionuclides has been developed for application to soil and sediment samples. The procedure was optimised using a reference sediment (IAEA-368) and reference soils (IAEA-375 and IAEA-326). Reference materials were first digested using acids (leaching), ‘total’ acids on hot plate, and acids in microwave in order to compare the different digestion technique. Then, the separation and purification were made by anion exchange resin and selective extraction chromatography: transuranic (TRU) and strontium (SR) resins. Natural and anthropogenic alpha radionuclides were separated by uranium and tetravalent actinide (UTEVA) resin, considering different acid elution medium. Finally, alpha and gamma semiconductor spectrometer and liquid scintillation spectrometer were used to measure radionuclide activities. The results obtained for strontium-90, cesium-137, thorium-232, uranium-238, plutonium-239+240 and americium-241 isotopes by the proposed method for the reference materials provided excellent agreement with the recommended values and good chemical recoveries. Plutonium isotopes in alpha spectrometry planchet deposits could be also analysed by ICPMS.     

Simple and rapid methods for on-site determination of radon and thoron in soil-gases for seismic studies

The determination of soil-gas anomalies especially ²²²Rn anomalies, are important to precisely locate fault traces, as well as to investigate earthquake precursors. In this paper, we have studied and compared new rapid methods for on site determinations of radon (²²²Rn), thoron (²²⁰Rn) and total radon (²²²Rn+²²⁰Rn) in soil-gas. These new techniques pump the soil-gas continuously from the soil through a simple sampling tube to the counting cell for one-minute with discarding the excess. Then, either four one-minute counting periods (5-minute technique) or nine one-minute counting intervals (10-minute technique) are followed immediately. In all the methods, conversely to Morse"s method, the first counting period (C1) was not employed for calculations. Three calculation methods for the five-minute technique, two for the ten-minute technique and a modified Morse"s method are compared with theoretical values and different real soil-gases with different radon/thoron ratios. The affect of different flow rates of soil-gases into the counting cell was also investigated. Finally, the ten-minute technique seems to be a little more accurate, but the 5-minute technique is much more suitable for seismic field studies when a much larger number of determinations are required in a short time.