Determination of129I and127I in environmental samples by neutron activation analysis (NAA) and inductively coupled plasma mass spectrometry (ICP-MS)

In order to assess the levels and behavior of¹²⁹I (half-life: 1.6×10⁷ y) and¹²⁷I (stable) in the environment, we have developed analytical procedures involving neutron activation analysis (NAA). Environmental samples collected around Tokaimura, Ibaraki Prefecture, Japan, have been analyzed using this method. Ranges of¹²⁹I and¹²⁷I concentrations in surface soil were 0.9–180 mBq kg^–1 and 1–60 mg kg^–1, respectively. Higher¹²⁹I concentrations were found in soil samples collected from coniferous forests, suggesting a contribution from tree canopies in the deposition of this nuclide. Most of the¹²⁹I in soil, was found to be retained in the first 10 cm. The¹²⁹I/¹²⁷I ratios in wheat fields were lower than those in rice paddy fields.A soil sample collected by IAEA from an area contaminated by the Chemobyl accident was also determined. The¹²⁹I concentration and the¹²⁹I/¹²⁷I ratio were 1.6 mBq kg^–1 and 1.7×10^–7, respectively. The¹²⁹I level in this sample was higher than the values obtained in areas far from nuclear facilities in Japan. It was suggested that the analysis of¹²⁹I in soils in the Chernobyl area may be useful in evaluating the¹³¹I levels at the time of the accident.Analyses of¹²⁹I and¹²⁷I by ICP-MS in water samples were also made. The analytical speed of this method was very high, i.e., 3 minutes for a sample. However, there is a sensitivity limitation for¹²⁹I detection due to interference from¹²⁹Xe with the¹²⁹I peak. The detection limits for¹²⁹I and¹²⁷I in water samples were about 0.5 mBq ml^–1 and 0.1 ng ml^–1, respectively.     

Iodine-129 in Thyroid Glands: A Sensitive Biological Marker of Fission Product Exposure

appeared in the Journal of Radioanalytical and Nuclear Chemistry, Vol. 243, No. 2 (2000) 467–472.During the electronic submission of the paper the file was damaged, and parts were left out. In order to correct this, we publish the correct paper as a whole.Iodine-129 may be no radiation hazard but it is a useful marker. Animal thyroids concentrate the isotope to 4 orders of magnitude greater than the intake. This results in a potential biological and physical indicator of radioactive contamination. Since 1943, ¹²⁹I/¹²⁷I ratio in animal thyroids from the Northern Hemisphere has increased 2 to 5 orders of magnitude. Since 1985, thyroids of deer, living near a nuclear reprocessing facility have contained ¹²⁹I which is 3 to 7 orders of magnitude greater than pre-nuclear levels. Limited measurements of ¹²⁹I in thyroids from the Southern Hemisphere have shown little increase. An appendix is presented to show that ¹²⁹I may be helpful to evaluate past radiation hazard from fission products.     

Determination of iodine-129 and iodine-127 in environmental samples collected in Japan

Analytical method for the determination of¹²⁹I and¹²⁷I in environmental samples has been developed by using radiochemical neutron activation analysis. The¹²⁹I levels in the samples such as soil (0.9–41 mBq/kg), precipitation (0.002–0.11 mBq/kg), pine needles (1.2–32 mBq/kg) and seaweed (<0.1–17 mBq/kg) collected near the nuclear facilities in Tokaimura were higher than those from the other areas in Japan. The highest¹²⁹I concentration was found in surface soil (0–5 cm), and the highest¹²⁹I/¹²⁷I ratios were found in pine needles and precipitation. The¹²⁹I/¹²⁷I ratio was higher in rice paddy soil than those in wheat field soil collected around Tokaimura, while the concentration of¹²⁹I somewhat higher in wheat field soil.     

129I in soil and grass samples around a nuclear reprocessing plant

Neutron activation analysis was used to determine¹²⁹I in soil and grass samples around a reprocessing plant. The method involved wet oxidation of samples, using chromic acid, followed by distillation, collection of iodine in alkaline solution, loading on Dowex-1, irradiation and post-irradiation purification steps. The -activity of¹³⁰I isotope of the purified samples was measured for quantitative determination of¹²⁹I. The experimental results showed that¹²⁹I and the¹²⁹I/¹²⁷I atomic ratio in soil samples varied from 1.09×10^–4 to 5.33×10^–3 pCi g^–1 and 0.10×10^–6 to 6.12×10^–6, respectively. Further, the geometric mean of soil-to-plant transfer factor (Bv) for¹²⁹I was found to be 0.16 which was comparable with other published values.     

Long-Lived Radioiodine in Japanese Environment

The amount of long-lived radioiodine, ¹²⁹I (half-life 1.57·10⁷ y) in the Japanese environment has been studied by measuring thyroids of humans and animals. The collected samples were thyroids of (1) humans in Ibaraki Prefecture, in Kanto district, the central part of Japan, (2) cattle in Aomori Prefecture, north part of Japan, and (3) wild deer in Chiba Prefecture, in Kanto district. The measured mean isotopic ratio ¹²⁹I/¹²⁷I for thyroids of cattle in Aomori Prefecture is 3.5±1.8·10^-9. A higher value of 14±5·10^-9 has been obtained for thyroids of wild deer in Kanto district. On the other hand, the measured ratio for human thyroids in Kanto district is 1±0.2·10^-9. This value is significantly lower than that of cattle thyroids in Aomori and also those reported for human thyroids in Europe and USA. The higher mean ratio for cattle thyroid in Kanto district is possibly explained by the influence of nuclear reprocessing plant. Lower mean ratio for human thyroid might be due to higher dietary intake of algae.     

Iodine-129 in Thyroid Glands: A Sensitive Biological Marker of Fission Product Exposure

Iodine-129 may have no radiation hazard but it is a useful marker. Animal thyroids concentrate the isotope to 4 orders of magnitude greater than the intake. This results in a potential biological and physical indicator of radioiodine contamination. Since 1943, ¹²⁹I/¹²⁷I ratio in animal thyroids from the Northern Hemisphere has increased 2 to 5 orders of magnitude. Since 1985, thyroids of deer living near a nuclear reprocessing facility have contained ¹²⁹I, which are 3 to 7 orders of magnitude greater than pre-nuclear levels. Limited measurements of ¹²⁹I in thyroids from the Southern Hemisphere have shown little increase. An appendix is presented to show that ¹²⁹I, may be helpful to evaluate past radiation hazard from fission products.     

Determination of 129I in biomonitors collected in the vicinity of a nuclear power plant by neutron activation analysis

Neutron activation analysis (NAA) was used to determine ¹²⁹I and the ¹²⁹I/¹²⁷I ratio in bovine thyroid, moss, and river sediment samples collected in the vicinity of the Temelín nuclear power plant (NPP) in south Bohemia. The NAA procedures comprised pre-irradiation separation of ¹²⁹I by combustion of the samples in the stream of oxygen at 1,000 °C and trapping the liberated iodine in a LiOH/(NH₄)₂SO₃ solution. Post-irradiation separation of ¹³⁰I produced by the reaction ¹²⁹I(n,γ)¹³⁰I was carried out by extraction of elementary iodine with chloroform followed by precipitation of PdI₂. Nondestructive, epithermal NAA was used to determine ¹²⁷I employing the ¹²⁷I(n,γ)¹²⁸I reaction. The results showed that mean values of ¹²⁹I and the ¹²⁹I/¹²⁷I ratio in the bovine thyroids varied from 22 to 61 mBq kg^?1 (dry mass) and 2.8 × 10^?9 to 5.4 × 10^?9, respectively. These values are close to the lower end of results reported from various regions non-polluted with ¹²⁹I. No significant differences were found between ¹²⁹I concentrations and the ¹²⁹I/¹²⁷I ratios in the bovine thyroids collected prior to the start and after several years of operation of the NPP. The mean value and standard deviation of ¹²⁹I in mBq kg^?1, dry mass and the ¹²⁹I/¹²⁷I ratio in moss Pleurozium schreberi were 23 ± 16 and 2.3 × 10^?9, respectively, whereas values of ¹²⁹I in the river sediments were below 8–10 mBq kg^?1 (dry mass) after several years of the NPP operation.     

A review on speciation of iodine-129 in the environmental and biological samples

As a long-lived beta-emitting radioisotope of iodine, ¹²⁹I is produced both naturally and as a result of human nuclear activities. At present time, the main part of ¹²⁹I in the environment originates from the human nuclear activity, especially the releases from the spent nuclear fuel reprocessing plants, the ¹²⁹I/¹²⁷I ratios have being reached to values of 10⁻¹⁰ to 10⁻⁴ in the environment from 10⁻¹² in the pre-nuclear era. In this article, we review the occurrence, sources, inventory, and concentration level of ¹²⁹I in environment and the method for speciation analysis of ¹²⁹I in the environment. Measurement techniques for the determination of ¹²⁹I are presented and compared. An overview of applications of ¹²⁹I speciation in various scientific disciplines such as radiation protection, waste depository, and environmental sciences is given. In addition, the bioavailability and radiation toxicity (dose to thyroid) of ¹²⁹I are discussed.     

Determination of I-129 and I-127 in soil and tracer experiments on the adsorption of iodine on soil

Neutron activation analysis of¹²⁹I and¹²⁷I in soil has been studied. The limit of detection for¹²⁹I in soil was about 0.05 mBq/kg or 1×10^–9 as¹²⁹I/¹²⁷I atom ratio. The range of¹²⁹I concentration in surface soils collected around Tokaimura (Ibaraki Prefecture) was 0.9–41 mBq/kg.Tracer experiments on the adsorption of iodine were also carried out, in order to obtain information on the behaviour of iodine in soil-water systems. Different adsorption patterns of iodide and iodate on soil were found. It was supposed that iodide was adsorbed by the soil fraction which became unstable at about 200° C and iodate by the fraction which was relatively stable to heating.     

Contribution of nuclear medicine procedures to global129I inventory

¹²⁹I content of batches of Na¹³¹I vials, used for nuclear medicine procedures, was estimated by neutron activation analysis. The average value of the¹²⁹I/¹³¹I activity ratio /corresponding to zero decay time of the latter/ was /4.98±2.8/x10^–9. It is concluded that the contribution of¹²⁹I from medical applications of¹³¹I in India is insignificant in relation to that from nuclear fuel cycle activities.     

Determination of 129I/127I ratios in environmental samplesusing neutron activation analysis

Studies on the behavior of ¹²⁹I in the environment are greatly enhanced when the concentration of the radioiodine can be related to stable ¹²⁷I. The background ratios of ¹²⁹I/¹²⁷I of 10^-10 and lower, found in uncontaminated areas, are best measured using accelerator mass spectrometry. However, there are many examples of studies where ratios higher than 10^-8 have been measured, even in places located remotely from nuclear reprocessing activities. In the vicinity of reprocessing plants it is possible to find ratios between 10⁰ and 10^-7, which can be detected easily using neutron activation analysis (NAA). Stable iodine is readily determined at concentrations below 1 mg/kg in environmental materials with instrumental NAA and radiochemical techniques can be used to measure ¹²⁹I to below mBq concentrations. Therefore, where there are elevated concentrations of ¹²⁹I it is possible to use a combination of neutron activation techniques to determine ¹²⁹I/¹²⁷I ratios. This paper describes how NAA is used to measure ¹²⁹I/¹²⁷I ratios in milk, vegetation, and atmospheric samples. Instrumental NAA is used to measure both ¹²⁹I and ¹²⁷I where the ratio is between 10⁰ and 10^-3. A radiochemical procedure is used to measure ¹²⁹I at ratios between 10^-3 and 10^-7, with a thermal neutron flux of 10¹⁶ m^-2·s^-1.     

129I levels in soils from Ukraine and Slovenia in the last decade

¹²⁹I is important as an environmental tracer of the biogeochemical cycling of iodine and of the dissemination of nuclear pollution, because anthropogenic ¹²⁹I has been released from only few point sources and with its short mixing time its distribution therefore reveals the movement of ¹²⁹I in the environment. A radiochemical neutron activation analysis method was developed to measure the concentration of ¹²⁹I in soil samples. A procedure to pre-concentrate iodine from up to 150?g of soil was developed and validated using IAEA standard reference material IAEA-375 (Chernobyl soil). The method was applied to determine ¹²⁹I/¹²⁷I isotopic ratios as well as ¹²⁹I and ¹²⁷I concentrations in soils from several locations in Ukraine collected in 2006, 1996, 1993 and 1989, and from Slovenia, collected at various places in 2009 and 2006. The ¹²⁷I concentrations in surface soils from Ukraine were in the range 2.3–23.1?µg?g^?1 and for ¹²⁹I (11.1–245.7)?·?10^?8?µg?g^?1 dry matter with the highest value of 1.47?·?10^?3?µg?g^?1 found in a soil sample collected in Yaniv, Ukraine in July 1993. In soil samples from Slovenia ¹²⁷I concentrations ranged 0.73–130?µg?g^?1 and ¹²⁹I (8.0–245.7)?·?10^?8?µg?g^?1. The ¹²⁹I/¹²⁷I isotopic ratios of surface soils from Ukraine were in the range of the order of 10^?9–10^?5 and of 10^?10–10^?8 for soils from Slovenia. The highest isotopic ratio 13.6?·?10^?5 was found in a soil sample collected in Yaniv, Ukraine in July 1993.     

Removal of iodooraganic compounds from kerosene in nuclear fuel reprocessing

A 10^–5 mol 1^–1 solutiopn of idododecane in n-dodecane was used to simulate a kerosene sample from nuclear fuel reporcessing. Several methods were developed for the quantitative removal of iodododecane from the n-dodecane solution. Decomposition to elemental iodine was achieved either by washing with hyperazeotropic nitric acid or by exposure to a high-intensity UV-light. Quantitative removal of iodododecane from n-dodecane was achieved by absorption on silver nitrate impregnated materila or on activated charcoal, which was impregnated with potassium thiocyanate or 1,4-diazabicyclo-2,2,2-octance. The reaction could be accelerated by stirring or heating. Thus a quantitative absorption of idododecane could be achieved within a few minutes. The results of the experiments were confirmed by absorption of iodoorganic compounds from kerosene of the Karl sruhe nuclear fuel reprocessing plant (WAK) on the tested material.     

Iodine separation procedure for the determination of129I and127I in soil by neutron activation analysis

A radiochemical neutron activation analytical method for the determination of¹²⁹I and¹²⁷I in soil samples was studied. Iodine was separated from the sample prior to the irradiation by volatilization, i.e. by combustion of the sample and trapping of the iodine in an alkaline solution together with a reducing agent. This method enables one to digest samples containing up to 100 g dry matter. The chemical yield was mostly more than 90%. After irradiation the iodine fraction was further purified by solvent extraction. The detection limit of the¹²⁹I/¹²⁷I ratio was 1×10^–9.     

Dry deposition velocity of iodine-129 onto grass as obtained by field measurements in the environment of a nuclear fuel reprocessing plant

The deposition velocity of gaseous organic¹²⁹I species from the exhaust air stack of the Karlsruhe reprocessing plant onto pasture grass was measured by a field experiment. By simultaneously measuring the amount of¹²⁹I deposited per unit area of pasture grass and the time integrated mean air concentration of¹²⁹I a deposition velocity of V_g=5.8×10^–1 /cm s^–1/ onto pasture grass was determined.     

(n, 2n) reactions in iodate and periodate systems

The chemical consequences of (n,2n) reactions on crystalline sodium iodates and sodium periodates, containing¹²⁷I or¹²⁷I+¹²⁹I, were investigated measuring the initial yields and the post irradiation thermal annealing yields at 90°C for three separated fractions: I+I^o, IO ₃ ^– and IO ₄ ^– . The results show different effects for each system and neither isotope effect nor qualitative differences on thermal annealing were observed. The influence of the nuclear reaction type, of the hot-atom's nature and of the structural and chemical environment are discussed.     

Search for neutrons from cold nuclear fusion

An attempt was made to detect neutrons from the so-called cold nuclear fusion of deuterium in palladium and titanium, both saturated with deuterium: the palladium electrolytically and the titanium from gas phase. The measurements were performed in a tunnel located 30 m deep in limestone, using³He filled proportional counters surrounded by water for neutron moderation. In all cases the detected neutron flux was practically equal to the background level. Very low upper limits to the neutron source strength were obtained from this experiment: 2×10^–4 n.s^–1g^–1 Pd and 4.3×10^–4 n.s^–1g^–1 Ti on the 1 level.     

Chemical and nuclear interferences in neutron activation of129I and127I in environmental samples

A combination of neutron activation and gamma-ray coincidence counting technique is used to determine the concentration of both long-lived fission produced¹²⁹I and natural¹²⁷I in environmental samples. The neutron reactions used for the activation of the iodine isotopes are¹²⁹I(n, )¹³⁰I and¹²⁷I(n, 2n)¹²⁶I. Nuclear interferences in the activation analysis of¹²⁹I and¹²⁷I can be caused by production of¹³⁰I or¹²⁶I from other constituents of the materials to be irradiated, i.e. Te, Cs and U impurities and from the¹²⁵I tracer used for chemical yield determination. Chemical interferences can be caused by¹²⁹I and¹²⁷I impurities in the reagents used in the pre-irradiation separation of iodine. The activated charcoals used as iodine absorbers were carefully cleaned. Different chemical forms of added¹²⁵I tracer and¹²⁹I and¹²⁷I constituents of the samples can cause different behaviour of¹²⁵I tracer and sample iodine isotopes during pre-irradiation separation of iodine. The magnitude of the nuclear and chemical interferences has been determined. Procedures have been developed to prevent or control possible interferences in low-level¹²⁹I and¹²⁷I activation analysis. For quality control a number of biological and environmental standard samples were analyzed for¹²⁷I and¹²⁹I concentrations.     

Levels of tritium concentration in the environmental samples around JAERI TOKAI

By the operation of research reactors, tritium-handling facilities, nuclear power plants, and a reprocessing facility around JAERI TOKAI, tritium is released into the environment in compliance with the regulatory standards.To investigate the levels of tritium concentration in environmental samples around JAERI, rain, air (vapor and hydrogen gas), and tissue-free water of pine needles were measured and analyzed from 1984 to 1993. Sampling locations were determined by taking into consideration wind direction, distance from nuclear facilities, and population distribution. The NAKA site (about 6 km west-northwest from the TOKAI site) was also selected as a reference point.Rain and tissue-free water of pine needles were sampled monthly. For air samples, sampling was carried out for two weeks by using the continuous tritium sampler. After the pretreatment of samples, tritium concentrations were measured by a low background liquid scintillation counter (detection limit is 0.8 Bq/l).Annual mean tritium concentrations in rain observed at six points for 10 years was 0.8 to 8.9 Bq/l, which decreased with distance from the nuclear facilities. Tritium concentrations in rain obtained at Chiba City were around 0.8 Bq/l (1987–1988) and those at the NAKA site were 0.8 to 3.8 Bq/l.Annual mean HTO concentrations in air at three points for 10 years were 9.2×10^–2 to 1.1 Bq/m³, although HT concentrations in air, ranging from 1.7×10^–2 to 5.8×10^–2 Bq/m³, were not influenced by the operation of the nuclear facilities.Annual mean tritium concentrations in tissue-free water of pine needles at four points for 10 years were 1.4 to 31 Bq/l. Those at the NAKA site ranging from 1.4 to 6.2 Bq/l were in good agreement with the reported value by Takashima of 0.78 to 3.0 Bq/l at twenty-one locations in Japan.Monthly mean HTO concentrations in air for 10 years showed a good correlation with absolute humidity, while other samples showed no seasonal variation.Higher level tritium concentrations in rain, in air (vapor), and in tissue-free water of pine needles at the TOKAI site were caused by the tritium released from the nuclear facilities.The committed effective dose equivalent to the member of general public, estimated using the maximum tritium concentration in air (1.1 Bq/m³), was 0.23 Sv, which was about 1/4000 of dose limit for general public.     

Dehydration kinetics of ulexite from thermogravimetric data

In the present study, the kinetic parameters of the thermal decomposition of ulexite were investigated by using TGA data. For the kinetic analysis, the Suzuki and Coats-Redfern methods were applied. It was determined that the process fits a first-order kinetic model, and the value of the activation energies and frequency factors decreased with decreasing particle size, which can be attributed to the increasing particle internal resistance to the escape of water as the grain size increases. The activation energy values were found to be 47.34–60.01 kJ mol^–1 for region I and 0.225–1.796 kJ mol^–1 for region II for the range of particle size fraction used. The frequency factors were calculated to be 9821.8–524.9 s^–1 for region I and 3.05×10^–44–2.807×10^–5 for region II for the same conditions.