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.     

Transfer of 137Cs and stable Cs in soil-grass-milk pathway in Aomori, Japan

The soil-to-grass transfer factors and grass-to-milk transfer coefficients were determined for ¹³⁷Cs and stable Cs in soil, grass and milk samples collected in Aomori Prefecture, Japan. The concentrations of ¹³⁷Cs in the soil and grass samples collected from 25 sampling sites were 13±12 Bq.kg^-1 and 2.0±2.1 Bq.kg^-1 dry wt., respectively. The geometric mean of soil-to-grass transfer factor of ¹³⁷Cs was 0.13 and its 95% confidence interval was 0.017-0.98. The transfer factor of ¹³⁷Cs was higher than that of stable Cs, and they had a positive correlation. The concentration of K in the soil affected both transfer factors. The concentration of ¹³⁷Cs in milk samples collected from 16 sites was 76±43 mBq.kg^-1 fresh wt. and had a good correlation with that of stable Cs. The geometric mean of grass-to-milk transfer coefficient of ¹³⁷Cs was 0.0027, assuming that a cow's total daily intake was 20 kg of dry grass. The transfer coefficient of ¹³⁷Cs was positively correlated with that of stable Cs.     

Determination of135Cs in sodium from an in-pile loop by activation analysis

Several months after shut-down,¹³⁷Cs and¹³⁴Cs were the main activities in coolant residues from an in-pile sodium loop where a fuel pin had failed at 40000 MWd/t burn-up, FR2-reirradiation of coolant residues increased¹³⁴Cs and generated¹³⁶Cs, thus indicating the presence of stable¹³³Cs and of long-lived¹³⁵Cs in the samples. The amount of¹³⁵Cs calculated from¹³⁶Cs activities was of the same quantity as the number of¹³⁷Cs atoms.     

Distribution of 131I, 134Cs, 137Cs and 239,240Pu concentrations in Korean rainwater after the Fukushima nuclear power plant accident

Radionuclides such as ¹³¹I, ¹³⁴Cs, ¹³⁷Cs, and ^239,240Pu in Korean rainwater have been analyzed by Korea Research Institute of Standards and Science (KRISS) since the Fukushima nuclear power plant accident in March 2011 to investigate the activity level, distribution pattern, and temporal variation and to assess the radiation dose the public is exposed to. The concentration of ¹³¹I in the Korean rainwater samples varied between 0.033 (minimum detectable activity; MDA) and 1.30 Bq kg^?1 and the concentrations tended to decrease exponentially with time. The concentrations of ¹³⁴Cs and ¹³⁷Cs in rainwater ranged from 0.01 to 334 ± 74 and 0.29 ± 0.01 to 276 ± 1 mBq kg^?1, respectively. The mean activity ratio of ¹³⁷Cs/¹³⁴Cs in the rainwater samples collected from April 18 to May 12 was estimated to be 0.44 ± 0.21, and this value is lower than that (ca. 1) observed in Fukushima, Japan, when there was an escape from the nuclear reactors. When an attempt was made to analyze Pu isotopes in rainwater samples, no Pu isotopes were detected above the MDA in any of the rainwater samples. Although the locations investigated were different from Asia to Europe, the concentrations of ¹³¹I, ¹³⁴Cs and ¹³⁷Cs in the rainwater are comparable, which suggests a global contamination of ¹³¹I, ¹³⁴Cs, and ¹³⁷Cs occurred because of the Fukushima nuclear power plant accident.     

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.     

Inventories of 239+240Pu, 137Cs, and excess 210Pb in sediment cores from brackish Lake Obuchi, Rokkasho Village, Japan

The aim of this study was to measure the distribution and inventories of ^239+240Pu, ¹³⁷Cs, and excess ²¹⁰Pb (²¹⁰Pb_excess) in sediment core samples from brackish Lake Obuchi, which is in the vicinity of nuclear fuel facilities in Rokkasho Village, Japan. The inventory of the ^239+240Pu activity in the sediment samples from the estuary of a freshwater river, the central point of the lake, and the deepest point in the lake were 0.18, 0.29, and 0.24 kBq·m^–2, respectively. The inventories of ¹³⁷Cs and ²¹⁰Pb_excess in sediments were 0.83–1.2 kBq·m^–2 and 25–30 kBq·m^–2, respectively. The mean ^239+240Pu/¹³⁷Cs and ²¹⁰Pb_excess/¹³⁷Cs activity ratios were 0.23 and 28, respectively. The^239+240Pu/¹³⁷Cs activity ratios were approximately 13–24 times the ratio expected from global fallout. The inventories of ^239+240Pu and ²¹⁰Pb in sediments were higher than the inventory expected from atmospheric fallout, but the ¹³⁷Cs inventory was significantly lower than expected.This revised version was published online in November 2005 with corrections to the Cover Date.     

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.     

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.     

Determination of 135Cs in nuclear power plant wastes by ICP-MS and k 0-NAA

A radiochemical method for the determination of ¹³⁵Cs in radioactive wastes has been adopted/developed. For the separation of cesium from other elements ammonium-molybdophosphate precipitation and cation exchange chromatography were used. The chemical yield of the method was about 60–100 %. ¹³⁵Cs was measured by two methods. In neutron activation analysis (NAA), Cs was irradiated with reactor neutrons. ¹³⁶Cs was detected by gamma spectrometry, wherefrom the activity/mass of ¹³⁵Cs was calculated according to the k ₀-standardization technique. The Cs containing fractions were measured by inductive coupled plasma mass spectrometry, as well. NAA and ICP-MS techniques were comparatively evaluated and a good agreement between the results was found. The activity concentration of ¹³⁵Cs in a couple of waste samples originating from VVER-440 type nuclear reactors was in the range of 1–5 Bq L^?1 (20–120 ng L^?1) while ¹³⁷Cs activity concentrations varied between 0.1 and 1 MBq L^?1.     

Rough localization of defective PWR fuel rods on the basis of the concentration ratio134Cs/137Cs in the primary coolant

The search for fuel assemblies with defective fuel rods by sipping tests involves expensive prolongations of the refuelling periods in nuclear power plants. It is attempted to reduce the number of fuel assemblies to be checked by sipping during the refuelling periods by means of rough localization of the defects on the basis of the fission product concentration ratio¹³⁴Cs/¹³⁷Cs in the primary coolant already during reactor operation. First results obtained in two examples of application at VVER type reactors are encouraging. The burnup of the defective assemblies could be correctly predicted from the cesium ratio in these two cases, which was confirmed by sipping tests after reactor shutdown.     

Dating of Black Sea sediments from Romanian coast using natural 210Pb and fallout 137Cs

The sediment samples collected near the shore from Romania were used for the determination of levels of natural ²¹⁰Pb, ²²⁶Ra and fallout ¹³⁷Cs radionuclides. The sediment samples were dried and ground to a fine powder. Airtight sealed samples were counted by gamma-spectrometer with 110 cm³ well-type HPGe detector for one week each. By using the isotopic analysis results, sediment accumulation rate was determined. A sedimentation rate of 0.20±0.01 cm^.y^-1 was determined using ²¹⁰Pb method and 0.15±0.03 cm^.y^-1 using ¹³⁷Cs isotope. Fallout peak from Chernobyl reactor accident, as well as the peaks due to nuclear tests, act as time markers.     

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.     

Application of Cu·FeHCF coated acrylic fibre for the separation of Cs isotopes in drinking water to determine fallout 137Cs

Ten fresh water samples of wells and rivers from the environment of Tarapur Maharashtra Site were analyzed to evaluate and establish the fall out level of ¹³⁷Cs activity concentration using large volume of water samples. A radiochemical separation method suitable for the analysis of large volume of water sample based on the adsorption of Cs isotopes on coated acrylic fibres was standardized. ¹³⁴Cs isotope was used for monitoring the radiochemical recovery of the analysis. Radiochemical recovery was obtained in the range of 74?C98% for a sample volume of 250?L or more. The fall out level ¹³⁷Cs concentration in river/dam water was found to be in the range of 0.205 to 0.268?mBq?L^?1. The fall out level annual effective dose through water ingestion pathway for a member of public was evaluated to be 2.27?×?10^?9?Sv.     

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.     

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.     

Accumulation of103Ru,137Cs and134Cs in fruitbodies of various mushrooms from Austria after the Chernobyl incident

Various mushrooms from Austria were analyzed for¹⁰³Ru,¹³⁷Cs and¹³⁴Cs after the reactor accident at Chernobyl /19.6.–26.10. 1986/ by -spectroscopy. The following concentration (nCi/kg wet weight) values were found:¹⁰³Ru 0.1–4 nCi/kg,¹³⁷Cs 0.5–104 nCi/kg,¹³⁴Cs 0.3–42 nCi/kg. The concentration of cesium isotopes in Cantharellus cibarius /lower Austria/, Leccinum scabrum /lower Austria/ and Xevocomus badius /lower Austria/ was considerably higher than in other mushroom samples.     

Determination of the balance of the nuclear reactor fuel burn-out process by gamma-spectrometry of fission products III

The possibility for the determination of heavy water reactor fuel burn-up on the basis of gamma-spectrometric measurements of the activity quotients¹⁰⁶Ru/¹³⁷Cs and¹³⁴Cs/¹³⁷Cs has been experimentally investigated. The investigation has been carried out on the non-enriched uranium metal fuel of the Czechoslovak Nuclear Power Plant Al. A spectrometer with germanium detector has been used for spectrum analysis of the irradiated fuel gamm-radiation. Burn-up has been determined (1) by the applied here procedure, and (2) from the results of mass-spectrometric determination of the isotopic composition and content of U, Pu and Nd. Two groups of the values obtained have been compared and the influence of the errors of the measured activity quotients on the established deviations has been evaluated.     

The determination of134Cs,137Cs,210Pb,226Ra and228Ra concentrations in nearshore marine sediments and seawater

Multi-radionuclide analyses of coastal marine sediments and seawater can be of considerable value in defining rates and mechanisms of nearshore processes. A preliminary study of¹³⁴Cs,¹³⁷Cs,²¹⁰Pb,²²⁶Ra and²²⁸Ra in the Clyde Sea Area has been performed. A summary of the marine geochemistries of these species and a detailed account of methods involved in their routine analysis are described.     

Determination of131I,134Cs,137Cs in plants and cheese after Chernobyl accident in Roumania

Various samples from the south-east region of Roumania/greens, fodder, cheese/were analyzed for¹³¹I,¹³⁴Cs and¹³⁷Cs concentrations in May and July 1986 by -ray spectrometry. The concentrations are reported in nCi. kg^–1 wet weight. For greens, a considerable decrease was observed for¹³¹I/to 3.0–7.0 nCi. kg^–1/,¹³⁴Cs/to 0.5–2.0 nCi.kg^–1/ and¹³⁷Cs /to 1.0–4.0 nCi. kg^–1/ from the first half /5–15 May/ till the end of May 1986. For cheese, maximum values were measured between 5 and 15 May /sheep cottage cheese: 500–800 nCi.kg^–1 for¹³¹I, 25–50 nCi. kg^–1 for¹³⁴Cs, 40–80 nCi. kg^–1 for¹³⁷Cs/; at the beginning of July a considerable decrease /to 5–10 nCi. kg^–1 for¹³¹I, 1.2–2.0 nCi.kg^–1 for¹³⁴Cs, 2.2–3.0 nCi. kg^–1 for¹³⁷Cs/ was observed. In autumn 1986 a small increase up to 2.0–3.0 nCi. kg^–1 for¹³⁴Cs and 3.4–5.0 nCi. kg^–1 for¹³⁷Cs /in November/ was reported. The population's internal possible contamination was strongly limited by the authorities' severe control of the food-stuff.     

Determination of Cs,Rb and Ba in neutron-activated biological materials

In the present paper, the determination of Cs, Rb and Ba in biological materials, including human bones, eggs, milk, meat and vegetables by neutron activation analysis is described. The proposed technique is based on the measurement of the long-lived radioisotopes¹³¹Ba,¹³⁴Cs and⁸⁶Rb with a Ge(Li) detector, after a simple radiochemical separation based on selective retention of these nuclides on HAP in 6M HF. Detection limits of 0.001 ppm can be achieved with 5% precision. Data are given for replicate determinations in six different types of materials.