Comparison of thermal ionization mass spectrometry and Multiple Collector Inductively Coupled Plasma Mass Spectrometry for cesium isotope ratio measurements

In the nuclear domain, precise and accurate isotopic composition determination of elements in spent nuclear fuels is mandatory to validate neutron calculation codes and for nuclear waste disposal. The present study presents the results obtained on Cs isotope ratio by mass spectrometric measurements. Natural cesium is monoisotopic (¹³³Cs) whereas cesium in spent fuels has 4 isotopes (¹³³Cs, ¹³⁴Cs, ¹³⁵Cs, and ¹³⁷Cs). As no standard reference material is available to evaluate the accuracy of Cs isotopic measurements, a comparison of cesium isotopic composition in spent nuclear fuels has been performed between Thermal Ionization Mass Spectrometry (TIMS) and a new method involving Multiple Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS) measurements. For TIMS measurements, isotopic fractionation has been evaluated by studying the behavior of cesium isotope ratios (¹³³Cs/¹³⁷Cs and ¹³⁵Cs/¹³⁷Cs) during the analyses. For MC-ICPMS measurements, the mass bias effects have been corrected with an external mass bias correction using elements (Eu and Sb) close to cesium masses. The results obtained by the two techniques show good agreement: relative difference on ¹³³Cs/¹³⁷Cs and ¹³⁵Cs/¹³⁷Cs ratios for two nuclear samples, analyzed after chemical separation, ranges from 0.2% to 0.5% depending on the choice of reference value for mass bias correction by MC-ICPMS. Finally the quantification of the ¹³⁵Cs/²³⁸U ratio by the isotope dilution technique is presented in the case of a MOx (mixed oxide) spent fuel sample. Evaluation of the global uncertainties shows that this ratio could be defined at an uncertainty of 0.5% (k = 2). The intercomparison between two independent mass spectrometric techniques is fundamental for the evaluation of uncertainty when no isotopic standard is available.     

Isotopenkorrelationen Mit Gammaaktiven Spaltprodukten für die Kernmaterialkontrolle von WWER-Brennstoff

Linear correlations between burnup, Pu/U- and U₅/U₀-ratios on the one hand and¹⁵⁴Eu/¹³⁷Cs or¹³⁴Cs/¹³⁷Cs ratios on the other hand have been proved to exist in the case of spent WWER fuel. The possibility of using such correlations for safeguards to determine the²³⁵U and Pu content of fuel assemblies has been demonstrated. The results agree well with theoretical calculations using the COFIP and COHN codes.      

Gamma-spectrometric determination of106Ru,134Cs,137Cs and144Ce in the fuel from the Czechoslovak atomic power station A-1

Determination of¹⁰⁶Ru,¹³⁴Cs,¹³⁷Cs and¹⁴⁴Ce in samples of irradiated fuel from the Czechoslovak atomic power station Al is described. The determination is based on gamma-spectrum analysis. The analysis was performed using a Ge(Li) semiconductor detector; for the determination of the isotope mentioned the lines in the energy interval from 400 to 1300 keV were used. The analyses of both dissolved and non-dissolved samples of the fuel were performed. The results of the determinations and their comparison are given in detail.     

Improvement of <Superscript>137</Superscript>Cs analysis in small volume seawater samples using the Ogoya underground facility

¹³⁷Cs in seawater is one of the most powerful tracers of water motion. Large volumes of samples have been required for determination of ¹³⁷Cs in seawater. This paper describes improvement of separation and purification processes of ¹³⁷Cs in seawater, which includes purification of ¹³⁷Cs using hexachloroplatinic acid in addition to ammonium phosphomolybdate (AMP) precipitation. As a result, we succeeded the ¹³⁷Cs determination in seawater with a smaller sample volume of 10 liter by using ultra-low background gamma-spectrometry in the Ogoya underground facility. ¹³⁷Cs detection limit was about 0.1 mBq (counting time: 10⁶ s). This method is applied to determine ¹³⁷Cs in small samples of the South Pacific deep waters.     

An intercomparison of sampling techniques for measurements of radiocaesium in upland pasture and soil

An intercomparison of sampling procedures used by five laboratories for the determination of radiocaesium in vegetation and peaty soil was carried out at two locations in Cumbria. The multiple sampling has given information on the homogeneity of the parameters studied at each location. The parameters comprise soil bulk densities, total deposition of¹³⁷Cs, deposition of¹³⁷Cs in three soil layers, biomass densities, concentrations of¹³⁷Cs in pasture, and activity ratios (¹³⁴Cs/¹³⁷Cs) in soil and vegetation. The determination of total deposition of¹³⁷Cs gave no indication of differences between the laboratories. The results from the soil profiles do indicate significant differences between laboratories. One laboratory using a coring technique observed difficulties during sampling due to compression of the soil. The coring technique should thus be avoided or applied with extreme care for the sampling of depth profiles in peaty soil. The results from the sampling of pasture show no indication of differences between the laboratories. For the parameters studied the observed variabilities across soil depths and locations range from 10% to 81% in terms of relative standard deviations. A comparison across all results at the two locations indicate a 50% higher field variability at one of the sites relative to the other.     

Mass selective separation applied to radioisotopes of cesium

A technique that uses the intrinsic mass‐based separation capability of a quadrupole mass spectrometer has been used to resolve spectral radiometric interference of two isotopes of the same element. In this work the starting sample was a mixture of ¹³⁷Cs and ¹³⁴Cs and was (activity) dominated by ¹³⁷Cs. This methodology separated and ‘implanted’ ¹³⁴Cs that was later quantified for spectral features and activity with traditional radiometric techniques. This work demonstrated a ¹³⁴Cs/¹³⁷Cs activity ratio enhancement of >4 orders of magnitude and complete removal of ¹³⁷Cs spectral features from the implanted target mass (i.e. 134). Copyright © 2016 John Wiley & Sons, Ltd.     

Rapid and sensitive determination of radiocesium (Cs-135, Cs-137) in the presence of excess barium by electrothermal vaporization-inductively coupled plasma-mass spectrometry (ETV-ICP-MS) with potassium thiocyanate as modifier

An electrothermal vaporization-inductively coupled plasma-mass spectrometric (ETV-ICP-MS) method based on selective volatilization of cesium with KSCN as modifier has been developed for determination of radiocesium, i.e. ¹³⁵Cs and ¹³⁷Cs, in the presence of isobaric barium. A 10000 times excess of barium, which was volatilized at a temperature of 1100?°C, resulted only in a 1% signal increase in the signal of mass 135 amu. The recommended concentration of KSCN is 0.3 mM, and pretreatment and volatilization temperatures are 400?°C and 1100?°C, respectively. A ramp time of 1 s is recommeded for the volatilization step. The achieved limit of detection for ¹³⁵Cs is 0.2 pg/mL (10 μBq/mL) and 4 fg (0.2 μBq) absolute for a sample volume of 20 μL. This means a limit of detection for ¹³⁷Cs of 0.2 pg/mL (0.6 Bq/mL) and of 4 fg (0.01 Bq) absolute. Signal variations of ¹³⁵Cs and ¹³⁷Cs, respectively, in spiked samples with various matrices were investigated.     

Determination of Cs and Cs in environmental samples: A review

Radionuclides of caesium are environmentally important since they are formed as significant high yield fission products (¹³⁵Cs and ¹³⁷Cs) and activation products (¹³⁴Cs and ¹³⁶Cs) during nuclear fission. They originate from a range of nuclear activities such as weapons testing, nuclear reprocessing and nuclear fuel cycle discharges and nuclear accidents. Whilst ¹³⁷Cs, ¹³⁴Cs and ¹³⁶Cs are routinely measurable at high sensitivity by gamma spectrometry, routine detection of long-lived ¹³⁵Cs by radiometric methods is challenging. This measurement is, however, important given its significance in long-term nuclear waste storage and disposal. Furthermore, the ¹³⁵Cs/¹³⁷Cs ratio varies with reactor, weapon and fuel type, and accurate measurement of this ratio can therefore be used as a forensic tool in identifying the source(s) of nuclear contamination. The shorter-lived activation products ¹³⁴Cs and ¹³⁶Cs have a limited application but provide useful early information on fuel irradiation history and have importance in health physics.     

Temporal and spatial variations of <Superscript>137</Superscript>Cs in the waters off a nuclear fuel reprocessing facility in Rokkasho,Aomori, Japan

Five survey cruises were carried out from 2004 to 2007 to determine ¹³⁷Cs concentrations in the water columns off Rokkasho Village, Aomori Prefecture, Japan, where the spent nuclear fuel reprocessing plant of Japan Nuclear Fuel Ltd has been undergoing test operation since March 2006. Seawater samples were collected with a large volume in situ filtration and concentration system at different depths in the water column. ¹³⁷Cs in particulate form could not be detected in the survey area. Dissolved ¹³⁷Cs showed temporal variation, especially in the surface water. Based on the results, it was concluded that no observable ¹³⁷Cs contamination was present in the investigated area. The distribution of ¹³⁷Cs concentrations was influenced by the mixing between the Tsugaru and Oyashio Currents.     

Separation of zirconium,niobium, cerium and ruthenium on chitin and chitosan columns for the determination of cesium in nuclear fuel solutions

Nuclear fuel solutions atpH=2.5 can be passed through 7×1 cm chitin or chitosan columns to fix the Zr, Nb, Ce and Ru radioisotopes. This rapid and quantitative separation clears the γ-ray spectrum of the solution from the main activity contribution and leaves the¹³⁷Cs spectrum alone for accurate Cs determination. The process can be extended to radioactive waste waters.     

Development and application of an eco-hydrodynamic model for radionuclides in a brackish lake: Case study of Lake Obuchi, Japan, bordered by nuclear fuel cycling facilities</p> </p>

Summary In order to evaluate the transport of ³H and ¹³⁷Cs radionuclides in semi-closed brackish Lake Obuchi, Japan, bordered by nuclear fuel cycling facilities, a 3D-lower-trophic eco-hydrodynamic model has been developed and validated. In a short-term prediction, ³H and ¹³⁷Cs activity levels in water should be in an agreement with field measurements. It became clear that the results depended on the mixing of fresh water and seawater in the model. Moreover, a short-term simulation estimated that most ³H and ¹³⁷Cs flowed to the ocean rather than remaining in the lake. Based on calculations over the past 50 years, a peak of ¹³⁷Cs in sediment was in 1963, when the maximum ¹³⁷Cs fallout was observed. The calculation showed a rapid decrease after that peak, however, the field measurement data gradually declined. This suggested that the process by which ¹³⁷Cs accumulated from the watershed to the lake was actually slower in the field than in the model calculations. The model may be successfully applied to a variety of different environmental situations as a generic tool for evaluating the concentration and migration of ³H and ¹³⁷Cs in a brackish lake.</p> </p>     

A complementary cesium coolant concentration ratio for localizing defective PWR fuel rods during reactor operation

Rough techniques for pinpointing defective fuel pins during actual reactor operation were developed for nuclear power plants. These techniques are based on various fission product concentration ratios. Here, a new cesium concentration ratio,¹³⁴Cs/¹³⁶Cs, was tested in combination with the more usual cesium ratio¹³⁴Cs/¹³⁷Cs. This new cesium ratio confirmed the conclusions drawn from the ratio¹³⁴Cs/¹³⁷Cs and provided some additional information on the location of the defective fuel rods. Application of this second cesium ratio improves the reliability of the rough localization method.     

Accumulation of137Cs by mushrooms from Rogozno area of Poland over the period 1984–1988

The concentration of naturally occurring⁴⁰K and¹³⁷Cs from fallout were determined in various mushrooms as well as in a few samples of forest soil from the same region over the period of 1984–1988. The¹³⁷Cs content in mushrooms before the reactor accident at Chernobyl was generally below 500 Bq kg⁻¹ dry matter, except Paxillus involutus /2700 Bq kg⁻¹/. A remarkable increase of the¹³⁷Cs activity /up to ten times/ was observed in 1986. For almost all examined species this activity remained basically at the same level for the next two years. No correlation between⁴⁰K and¹³⁷Cs in mushrooms has been found.     

137Cs activity in surface water in the western North Pacific

Temporal and spatial variations of ¹³⁷Cs activity in surface waters in the western North Pacific are examined along the 165°E transect. ¹³⁷Cs in seawater of the western North Pacific has been introduced by global fallout originating from atmospheric nuclear weapons tests, which caused major fallout in the early 1960's. At this time ¹³⁷Cs activities in the surface waters in mid latitudes of the North Pacific were 10–20 Bq·m^-3. South of 30°N, ¹³⁷Cs activity decreased gradually towards the south. The surface ¹³⁷Cs activity was about 5 Bq·m^-3 in the Equatorial region. In the 1970's, the difference in ¹³⁷Cs activities in surface water between mid latitudes and the Equatorial region became smaller. The ¹³⁷Cs activity in surface water at 40°N – Equatorial region was almost constant at the level of 1.7–3.7 Bq·m^-3 in the late 1990's. In the Equatorial region, the ¹³⁷Cs activity in surface water showed no temporal change except for radioactive decay over these four decades. The surface ¹³⁷Cs level was 1.4–1.8 Bq·m^-3 in the north subarctic region around 50°N in the late 1990's. The lower ¹³⁷Cs activity may have been caused by deeper convection in this sea area and dilution by fresh water flux.     

Resuspension processes controll variations of 137Cs activity concentrations in the ground-level air

The ¹³⁷Cs activity concentration in the surface air between 1977 and 2007 was decreasing with an ecological half-life of 3.4?years, however, during 2007?C2010 the yearly averaged ¹³⁷Cs activity concentrations were almost constant. The increased atmospheric ¹³⁷Cs and ⁴⁰K levels observed during the winter may be due to surface soil resuspension and radionuclide transport by winds, particularly from open agricultural areas, as confirmed by high correlation coefficient between ¹³⁷Cs and ⁴⁰K atmospheric levels (R?=?0.84), and similar ¹³⁷Cs/⁴⁰K activity ratios in aerosols (0.07) and soils (0.05).     

Determination of137Cs and90Sr in milk by the static method with an ion exchanger

This paper presents the method of⁹⁰Sr and¹³⁷Cs determination from 10 litres of milk. The preconcentration is made by the static method with a strong acid cation exchanger (OSTION KS).¹³⁷Cs from the eluent (8M HCl) is selectively eliminated with ammonium molybdophosphate and then the^137mBa gamma activity measured, using NaI(T1) detector.⁹⁰Sr as⁹⁰Y is determined after achievement of the radioactive equilibrium and measured by flow proportional counter. The method appears to be accurate, reproducible and permits to determine³² mBq¹³⁷Cs and 13 mBq⁹⁰Sr in the samples.     

Radioactivity in the Exclusive Economic Zone of east coast Peninsular Malaysia: distribution trends of <Superscript>137</Superscript>Cs in surface seawater

Large volumes of surface seawater samples were collected from thirty locations in the Exclusive Economic Zone (EEZ) of the east coast Peninsular Malaysia on June 2008 to study the activity concentrations of ¹³⁷Cs. The results will serve as additional information to the existing baseline data and is very useful for monitoring fresh input of anthropogenic radionuclide into Malaysian marine environment. In this study, the activity concentrations of ¹³⁷Cs were determined using co-precipitation technique, followed by Gamma Spectrometry measurement. The mean activity concentration of ¹³⁷Cs ranged between 3.40 and 5.89 Bq/m³. Higher activity concentrations were observed at the coastal and towards the south of Peninsular Malaysia and were aligned with the high turbidity. These may due to the rapid diffusion of ¹³⁷Cs from suspended particulates and fine sediments into surface seawater. The activity concentrations of ¹³⁷Cs observed in this study were slightly higher than the concentrations reported in seawater at the Straits of Malacca, Vietnam and Philippines. This might be because the study area received more input of ¹³⁷Cs that originated from global fallout and then deposited on land which later being transported subsequently into the coastal zone due to siltation and erosion processes. It could also be attributed to the intrusion of river waters containing higher concentrations of ¹³⁷Cs.     

Simultaneous determination of60Co,131I and137Cs in model radioactive waste water by reverse radiometric flow injection analysis with the aid of a multichannel analyzer

Reverse radiometric flow injection analysis was used for the simultaneous determination of⁶⁰Co,¹³¹I and¹³⁷Cs in model radioactive waste water. A NaI (Tl) scintillation detector coupled to a Canberra MCA was used for measuring the activity of¹³⁷Cs at 662 keV,⁶⁰Co at 1173 keV and 1332 keV, and¹³¹I at 364 keV.     

Concentrations of 137Cs and 40K radionuclides and some heavy metals in soil samples from the eastern part of the Main Ridge of the Flysch Carpathians

The aim of the study is to present the results of determination of radioactivity of artificial ¹³⁷Cs and natural ⁴⁰K and certain heavy metals in soil samples collected from the eastern part of the Main Ridge of Carpathians, including the Beskid Niski Mts and the Bieszczady Mts. The evaluation of level of radionuclides was based on the bulk density analysis of the soil. A valuable finding of the study was a good linear correlation between the level of ¹³⁷Cs concentration and bulk density of the soil as well as an inverse correlation between radioactivity of natural ⁴⁰K and tested soil density. This might indicate though a high competitiveness of these elements between each other. Moreover, a good correlation between the concentrations of artificial element ¹³⁷Cs and Pb has been also observed in soil samples collected from the Beskid Niski Mts. In most cases, the level of artificial ¹³⁷Cs was lower comparing to an average ¹³⁷Cs concentration established for soils in Poland.     

Study on the preparation of a137Cs/137mBa radionuclide generator

^137mBa has been applied successfully to dynamic studies for diagnosis in nuclear medicine for a long time. A variety of inorganic exchangers have been employed for the separation of^137mBa from its parent¹³⁷Cs. In the present study, cupric cobaltic ferrocyanide and amorphous zirconyl phosphate were synthesized and compared for use in a¹³⁷Cs/^137mBa generator. The results show that the former can adsorb¹³⁷Cs more efficiently and provide high elution yield of^137mBa with greater than 99.99% radionuclide purity. A new generator involving multimillicuries of^137mBa, in connection with a computerized detection system, has been constructed.