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.     

Rapid determination of Cs and precise Cs/Cs atomic ratio in environmental samples by single-column chromatography coupled to triple-quadrupole inductively coupled plasma-mass spectrometry

For source identification, measurement of ¹³⁵Cs/¹³⁷Cs atomic ratio not only provides information apart from the detection of ¹³⁴Cs and ¹³⁷Cs, but it can also overcome the application limit that measurement of the ¹³⁴Cs/¹³⁷Cs ratio has due to the short half-life of ¹³⁴Cs (2.06 y). With the recent advancement of ICP-MS, it is necessary to improve the corresponding separation method for rapid and precise ¹³⁵Cs/¹³⁷Cs atomic ratio analysis. A novel separation and purification technique was developed for the new generation of triple-quadrupole inductively coupled plasma-mass spectrometry (ICP-MS/MS). The simple chemical separation, incorporating ammonium molybdophosphate selective adsorption of Cs and subsequent single cation-exchange chromatography, removes the majority of isobaric and polyatomic interference elements. Subsequently, the ICP-MS/MS removes residual interference elements and eliminates the peak tailing effect of stable ¹³³Cs, at m/z 134, 135, and 137. The developed analytical method was successfully applied to measure ¹³⁵Cs/¹³⁷Cs atomic ratios and ¹³⁵Cs activities in environmental samples (soil and sediment) for radiocesium source identification.     

Thermal neutron cross section and resonance integral of the reaction of135Cs(n,γ)136Cs: Fundamental data for the transmutation of nuclear waste

To determine the cross sections of the¹³⁵Cs(n,γ)¹³⁶Cs reaction, a sample of¹³⁵Cs included in a “standardized solution” of¹³⁷Cs was used as a target and irradiated in a reactor. The ratio of the atom number of¹³⁵Cs to that of¹³⁷Cs was determined to be 0.89±0.03 with a quadrupole mass spectrometer. The thermal cross section and the resonance integral measured in this study were determined to be 8.3±0.3 and 38.1±2.6 b respectively.     

Radionuclide concentration in sewage sludge at several location in Austria after the Chernobyl accident

The concentration of the radionuclides¹⁰³Ru,¹³⁴Cs and¹³⁷Cs in sewage sludge samples which were collected between July and September 1986, were measured by -ray spectrometry. High concentration of¹⁰³Ru,¹³⁴Cs and¹³⁷Cs were found in sewage sludge samples from Lower-Austria /Scheibbs, Zwettl/ and Styria /Eisenerz, Leoben/. the radioactivity concentration of¹³⁷Cs was two times higher than that of¹³⁴Cs. Following concentration values were found:¹⁰³Ru 0.1–63.0 nCi kg^–1,¹³⁴Cs 0.3–41.6 nCi kg^–1, and¹³⁷Cs 0.3–83.3 nCi kg^–1. The activity of these nuclides decreased from July 1986 to September 1986.     

The distribution and behaviour of artificial radionuclides in sediments of the north Wales coast,U.K.

The distribution of¹³⁴Cs,¹³⁷Cs and²¹⁴Am in surface and core sediments from areas in north Wales has been investigated. Coastal sites show a predominance of Sellafield-derived material for all three radionuclides whereas estuarine sites show an increased proportion of Chemobyl-derived caesium present. By the use of the¹³⁴Cs/¹³⁷Cs ratio, a mean proportion of Chemobyl-derived¹³⁷Cs in surface sediments collected in 1991 fell from 34% at an estuarine site to 11% at a coastal site. In deeper sections of cores representing sedimentation dates near the Chemobyl accident, up to 90% of¹³⁷Cs at the estuarine site and 26% at the coastal site can be attributed to Chemobyl. By using the position of the Chemobyl¹³⁴Cs and¹³⁷Cs peak in the cores, sedimentation rates of 0.7 mm·a^–1 were calculated.     

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.     

Determination of90Sr and137Cs in mushrooms following the Chernobyl fallout

After the Chernobyl accident high concentrations of radionuclides were found in Sweden in mushrooms and the contents of⁹⁰Sr and¹³⁷Cs were measured. The level of⁹⁰Sr was generally low and, in proportion to¹³⁷Cs, 2–3 orders of magnitude lower than in the fallut. The contents of¹³⁷Cs varied among species and extreme local variations occurred. The ratio¹³⁴Cs/¹³⁷Cs diverged from other biological samples leading to the conclusion that old fallout was involved in the uptake.     

A simple preparation of calibration curve standards of134Cs and137Cs by serial dilution of a standard reference material

Two sets of calibration standards for¹³⁴Cs and¹³⁷Cs were prepared by small serial dilution of a natural matrix standard reference material, IAEA-154 whey powder. The first set was intended to screen imported milk powders which were suspected to be contaminated with¹³⁴Cs and¹³⁷Cs. Therefore the concentration range of the calibration standards were about 40–400 Bq/kg. The precision of the preparation of the standard with about 7 Bq/kg of¹³⁴Cs and 39 Bq/kg of¹³⁷Cs at measurement time was 7.4% and 3.2%, respectively. The preparation of a similar standard by spiking the matrix with radioisotope solutions resulted in a poorer precision, about double that of the former technique. The other set of calibration standards was prepared to measure the environmental levels of¹³⁷Cs in commercial Venezuelan milk powders. Their concentration ranged from 3–10 Bq/kg of¹³⁷Cs. The accuracy of these calibration curves was checked by using IAEA-152 and A-14 milk powders. Their measured values were in good agreement with their certified values. Finally, it is shown that these preparation techniques by serial dilution of a standard reference material were simple, rapid, precise, accurate and cost-effective.This work was partly funded by a research contract PC-075 from the Consejo Nacional de Investigaciones Científicas y Tecnológicas (CONICIT).     

Migration of fission product137Cs in mud near a nuclear reactor

Due to the mismanagement of nuclear waste as well as heat exchanger degradation for the primary coolant of the one megawatt nuclear research reactor, the fission product¹³⁷Cs has been leaking to the environment ever since 1969. In the past thirty years, the long-lived¹³⁷Cs was accumulated and eventually trapped in the mud of the discharge pond right in front of the waste storage and the reactor facility. The distribution of¹³⁷Cs in mud was measured and contour-mapped to reveal the migration of trace levels of¹³⁷Cs in a period of three decades.     

Half-life of134Cs determined by gamma spectrometry

The half-life of¹³⁴Cs obtained by gamma spectrometry from the change of the¹³⁴Cs to¹³⁷Cs activity ratio is 2.04±0.03 years.     

A new gamma spectral analysis algorithm for the determination

The aim of the investigation was to determine whether the ¹³⁷Cs contamination found in plants around the Paks Nuclear Power Plant in Paks, Hungary was a result of local emission or of the earlier Chernobyl accident. We distinguished between the two possibilities on the basis of the ¹³⁴Cs/¹³⁷Cs ratio. The ¹³⁴Cs activities to be measured were extremely low, in some cases undetectable with conventional evaluation softwares. Therefore a special algorithm was used to determine the ¹³⁴Cs/¹³⁷Cs ratio. On the basis of the results it is evident, that the contamination originated from Chernobyl.     

The ambient gamma dose-rate and the inventory of fission products estimations with the soil samples collected at Canadian embassy in Tokyo during Fukushima nuclear accident

In this study, soil samples were collected at Canadian embassy in Tokyo (about 300 km from Fukushima) on 23 March and 23 May of 2011 for purposes of estimating concentrations of radionuclides in fallout, the total fallout inventory, the depth distribution of radionuclide of interest and the elevated ambient gamma dose-rate at this limited location. Some fission products and actinides were analyzed using gamma-ray spectrometry, alpha spectrometry and liquid scintillation counting. The elevated activity concentration levels of ¹³¹I, ¹³²I, ¹³⁴Cs, ¹³⁷Cs, ¹³⁶Cs, ¹³²Te, ¹²⁹mTe, ¹²⁹Te, ¹⁴⁰Ba and ¹⁴⁰La were measured by the gamma-ray spectrometer in the first sample collected on 23 March. Two months after the accident, the ¹³⁴Cs and ¹³⁷Cs became only detectable nuclides. A mass relaxation depth of 3.0 g/cm² was determined by the activities on the depth distribution of ¹³⁷Cs in a soil core. The total fallout inventory was thus calculated as 225 kBq/m² on March sampling date and 25 kBq/m² on May sampling date. The ambient gamma dose-rates in the sampling area estimated by the fallout fission products inventory and ¹³⁷Cs depth distribution ranged from 184 to 38 nGy/h. There was no detectable americium or plutonium in the soil samples by alpha spectrometry. Although ⁹⁰Sr or ⁸⁹Sr were detected supposedly as a result of this accident, it was less than the detection limit, which was about 0.4 Bq/kg in the soil samples.     

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.     

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.     

Determination of137Cs and134Cs in air samples collected near Belgrade /Yugoslavia/ following the Chernobyl accident

This paper presents the results of measurements of¹³⁷Cs and¹³⁴Cs content in air sampled during May 1986. Maximum concentrations:¹³⁷Cs 2.94±0.01 Bq m^–3 and¹³⁴Cs 1.38±0.01 Bq m^–3 were registered on May 3. Several other long lived radionuclides having -energies in the region 33 keV to 1365 keV were registered in the same samples two years later. The results of measurements of the total -activity in air for the same period are also presented.     

Radionuclide concentrations in several seaweeds and their annual variations

To examine the radionuclide concentrations in the environment, seaweeds were collected once a year since 1976 at two different places. A marked change was observed in the number of radionuclides in seaweeds. The increase of radionuclides is attributed to contamination by radioactive fallout from Chinese nuclear explosion tests. The radionuclide concentrations were strongly dependent on the species of seaweeds. A gradual decrease of the¹³⁷Cs/⁴⁰K activity ratio was observed in spite of the input of additional¹³⁷Cs fallout from Chinese nuclear tests. This implies that the amounts of¹³⁷Cs introduced into seawater by these detonations were small in comparison with those already contained in seawater. The cesium content in seawater was estimated by using specific activities of¹³⁷Cs in seaweeds and¹³⁷Cs concentration in seawater. The results show good agreement with the reported values by direct analysis of seawater.     

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.     

Computerized on-line measurement the yield of short-lived bromine and iodine isotopes from thermal neutron fission of235U

The short-lived bromine and iodine isotopes from thermal neutron fission of²³⁵U have been separated from fission products by one step solvent extraction combined with an ion exchange fast chemistry system. The measured gamma spectra have been acquisited by an automatic computer on-line system. The results include experimental independent fission yields of⁸⁶Br,^134mI,^134gI,^136mI, and^136gI, the cumulative yields of⁸⁷Br,⁸⁸Br,¹³⁷I,¹³⁸I. The isomeric yield ratio of¹³⁴I and¹³⁶I has been determined and the iodine isotopic distribution curve has been constructed and analyzed.     

Activities evolution of Chernobyl103Ru,134Cs and137Cs in Cluj fallout

The evolution of Chernobyl¹⁰³Ru,¹³⁴Cs and¹³⁷Cs in accumulated fallout is rigorously followed. The¹⁰³Ru activity of about 12 kBq.m^–2 in the middle of May 1986 became insignificant at the end of 1986, while the levels of¹³⁴Cs and¹³⁷Cs have changed during 3 years from 2.5 kBq.m^–2, respectively, 5 kBq.m^–2 to about 0.9 kBq.m^–2, respectively 4.7 kBq.m^–2 according to their proper half-lives.     

Determination of131I,134Cs,137Cs in grass and cheese after Chernobyl accident in Austria

Various samples from Styria /grass/ and Salzburg /cheese/ were analyzed for¹³¹I,¹³⁴Cs and¹³⁷Cs concentration during April–July 1986 by -ray spectrometry. The concentrations are reported in nCi kg^–1 wet weight. The concentration values found for¹³¹I 0.2–17.2 nCi kg^–1 /grass/, 0.1–0.5 nCi kg^–1 /cheese/, for¹³⁴Cs 1.1–6.2 nCi kg^–1 /grass/, 0.2–1.3 nCi kg^–1 /cheese/, for¹³⁷Cs 1.6–15.7 nCi kg^–1 /grass/, 0.3–2.2 nCi kg^–1 /cheese/. While radioactivity of¹³¹I,¹³⁴Cs and¹³⁷Cs in cheese samples increases from May to June, it decreases in grass samples from May to July 1986.