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.     

k 0-RNAA used in determination of 129I in a mixed resin sample

A k ₀-RNAA procedure was developed to determine ¹²⁹I in a mixed resin sample. CH₄ extraction and (NH₄)₂SO₃ back-extraction were used to separate ¹²⁹I in ashed samples. The ¹²⁹I target sample for irradiation in the reactor was prepared by heating the (NH₄)₂SO₃ back-extraction solution to reduce its volume and then to dry it in a quartz ampoule. No MgO and LiOH were needed during the target sample preparation. After irradiation, the nuclide ¹³⁰I was purified by combining hydrated antimony pentoxide column and CH₄ extraction separations. A k-factor was determined for the reaction of ¹²⁷I (n, 2n) ¹²⁶I and used for iodine chemical yield determination. The apparent ¹²⁹I concentrations of five nuclear reaction interferences were calculated. The relative standard deviation of three ¹²⁹I determinations was found to be 3.5 %. The ¹²⁹I content in the analyzed resin was found to be 1.36 × 10^?9 g/g (8.63 × 10^?3 Bq/g) with a relative uncertainty of 9.1 %. The detection limit of ¹²⁹I was calculated to be 7.4 × 10^?13 g (4.7 × 10^?6 Bq) in a k ₀-RNAA of a blank sample.     

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.     

Determination of 129I in cement-solidified radwastes using neutron activation

The purpose of this study is to develop a neutron activation method to determine trace amounts of ¹²⁹I in cement-solidified radwastes. The radwaste samples were alkaline fused using KOH and then ¹²⁹I and iodine carrier were chemically separated by solvent extraction before and after neutron irradiation. Both stable iodine (¹²⁷I) and ¹²⁹I can be activated by neutrons through ¹²⁷I (n, 2n) ¹²⁶I and ¹²⁹I (n, γ) ¹³⁰I reactions; their activated radionuclides were counted together with a high-purity germanium detector. The chemical recovery yields ranged from 30 to 60 %, and it was found that more than 99.9 % of interfering radionuclides can be removed using solvent extraction after neutron irradiation. The minimum detectable amounts can be lowered to less than 1 mBq g^?1, which is superior to low energy γ-ray spectrometry by a factor of >10², on average. The established technique can be applied to re-evaluation of ¹²⁹I content in radwastes that can be re-classified to lower classes, and the cost for designing a final disposal facility can be significantly reduced.     

Assessment of the relationships between iodine isotopes (127I, 129I) and atmospheric elements in precipitation from Sweden

In order to assess the relationships between iodine isotopes (¹²⁷I, ¹²⁹I) and atmospheric elements, the concentrations of chlorine and bromine were determined using high resolution inductively coupled plasma mass spectrometry with an X SeriesII ICPMS (Thermal Electron Corporation) machine for precipitation samples collected during the period 2000–2006 at three different stations (Abisko, Uppsala and Kvidinge) in Sweden. For concentration of chlorine, Abisko in the north has the lowest average concentration, 0.6 mg/L, Kvidinge showing a little higher, 1.13 mg/L, and Uppsala exhibits as the highest concentration, 2.93 mg/L. As to bromine, the median concentration was 3.07, 3.43 and 4.73 μg/L for station Abisko, Uppsala and Kvidinge, respectively. Chlorine and bromine show the highest correlation with ¹²⁷I in Kvidinge (r < 0.7) than those in Uppsala and Abisko. The different correlations of ¹²⁷I–Cl and ¹²⁹I–Cl, or ¹²⁷I–Br and ¹²⁹I–Br are attributed to their respective sources to the atmosphere. Furthermore, the results show that iodine isotopes (¹²⁷I, ¹²⁹I) have high correlations with Cl and Br than the other atmospheric elements.     

Correlation between iodine isotopes (129I and 127I) species and marine parameters in the Baltic Sea

Iodine is a bio-intermediate and redox-sensitive element in the oceans and understanding the relationship between transformation of iodine species promotes them as indicators of biochemical cycling in the ecosystems. To gain an insight into the transformation of iodine species, correlations between the iodine species (¹²⁷IO₃ ^?, ¹²⁷I^?, ¹²⁹I^?, ¹²⁹IO₃ ^?) and marine parameters (temperature, salinity, oxygen, total phosphorus, nitrate and ammonium) are assessed here for the Baltic Sea during different seasons. The datasets used cover the periods of August 2006, April 2007 and November 2009. The results indicate that the correlations between radioactive ¹²⁹I, stable ¹²⁷I species and marine parameters mainly response to their respective sources as well as oceanographic environments. Also, insignificant correlations of iodine species and nutrients data (total phosphorus, nitrate and ammonium) are observed, suggesting that transformation activity of iodine species in the Baltic Sea is not directly linked to biological production.     

Depth profiles of 129I species in the Bothnian Sea

The Bothnian Sea which is located between Finland and Sweden represents an important source of fresh water to the Baltic Sea. We here present new data on the radioactive isotope ¹²⁹I species from water samples collected in December 2009 at different depths in the Bothnian Sea. Concentrations of ¹²⁹I^? (iodide) in the Bothnian Sea range from 14 × 10⁸ to 32 × 10⁸ atoms/L, while ¹²⁹IO₃ ^? (iodate) concentrations are relatively low and fluctuating at 1 × 10⁸ atoms/L. For nutrients data determined in the same samples as ¹²⁹I, significant correlations could be found between ¹²⁹I^? and total P, NO₃–N, SiO₃–Si, but rather poor with NH₄–N. The correlations suggest comparable source pathway of ¹²⁹I^? and nutrient parameters, while the source of NH₄–N may be different. The small amounts and negligible change of ¹²⁹IO₃ ^? indicate prevailing extensive reduction of iodate in the Baltic Sea.     

Analysis of low-level 129I in brine using accelerator mass spectrometry

An improved solvent extraction procedure for iodine separation from brine samples has been applied at Xi’an Accelerator Mass Spectrometry (AMS) center. Oil in the brine sample has to be removed to avoid appearance of the third phase during solvent extraction and to improve the chemical yield of iodine. The small amount of oil remained in the water phase was first removed by phase separation through settling down sufficiently based on their immiscibility, and then by filtration through a cellulose filter, on which oil was absorbed and removed. After oil removed, extraction recovery of iodine could achieve more than 90 %. The sodium bisulfite as an effective reductant should be added before acidification to avoid loss of iodine by formation of I₂ in sample via reaction of iodate and iodide at pH 1–2, and then pH was adjusted to 1–2 to reduce the iodate to iodide followed by oxidation of iodide to I₂ and solvent extraction to separate all inorganic iodine. As a pre-nuclear era sample, ¹²⁹I/¹²⁷I ratio in brine is normally more than two orders of magnitude lower than that in present surface environmental samples, so prevention of cross-contamination and memory effect in apparatus during processing procedure are very critical for obtaining reliable results, and monitoring the procedure blank is very important for analytical quality of ¹²⁹I. The ¹²⁹I/¹²⁷I isotopic ratio in the brine samples and procedure blank of iodine reagents were measured to be (1.9–2.7) × 10^?13 and 2.08 × 10^?13, respectively, 3–4 orders of magnitudes lower than that in environmental samples in Xi’an, and the result of procedure blank is in the same level as the previous experiments in past 3 years, indicating contamination is not observed in our method.     

Certified reference material IAEA-418: 129I in Mediterranean Sea water

A certified reference material designed for the determination of ¹²⁹I in seawater, IAEA-418 (Mediterranean Sea water) is described and the results of certification are presented. The median of ¹²⁹I concentration with 95% confidence interval was chosen as the most reliable estimates of the true value. The median, given as the certified value, is 2.28 × 10⁸ atom L^?1 (95% confidence interval is (2.16–2.73) 10⁸ atom L^?1), or 3.19 × 10^?7 Bq L^?1 (95% confidence interval is (3.02–3.82) × 10^?7 Bq L^?1). The material is intended to be used for standardization procedures applied in accelerator mass spectrometric laboratories. It is available in 1 L units and may be ordered via IAEA web side (www.iaea.org).     

Occurrence,evolution and degradation of heavy haze events in Beijing traced by iodine-127 and iodine-129 in aerosols

Heavy haze events have become a serious environment and health problem in China and many developing countries, especially in big cities, like Beijing. However, the factors and processes triggered the formation of secondary particles from the gaseous pollutants are still not clear, and the processes driving evolution and degradation of heavy haze events are not well understood. Iodine isotopes (¹²⁷I and ¹²⁹I) as tracers were analyzed in time series aerosol samples collected from Beijing. It was observed that the ¹²⁷I concentrations in aerosols peaked during the heavy haze events. The conversion of gaseous iodine to particular iodine oxides through photochemical reactions provides primary nuclei in nucleation and formation of secondary air particles, which was strengthened as the external iodine input from the fossil fuel burning in the south/southeast industrial cities and consequentially induced heavy haze events. Anthropogenic ¹²⁹I concentrations peaked during clean air conditions and showed high levels in spring and later autumn compared to that in summer. ¹²⁹I originated from the direct air discharges and re-emissions from contaminated seawaters by the European nuclear fuel reprocessing plants was transported to Beijing by the interaction of Westerlies and East Asian winter monsoon. Three types of mechanisms were found in the formation and evolution of heavy haze events in Beijing by the variation of ¹²⁷I and ¹²⁹I, i.e., iodine oxides intermediated secondary air particles, dust storm and mixed mode by both secondary air particles and dust storm induced processes.     

129I assessment reveals the impact of Fukushima incident on Dapeng Peninsula,Shenzhen, China

In order to assess the radioactive impact of Fukushima Incident on the coastal environment of Dapeng Peninsula, Shenzhen, China, combining accelerator mass spectrometry with epithermal neutron activation analysis, we measured the ¹²⁹I/¹²⁷I ratios and ¹²⁹I levels in surface seawater, oyster (Ostrea gigas) and kelp (Sargassum henslouianum). The results showed that the influence of Daya Bay Nuclear Power Base was ignorable to local environment, but the Fukushima Incident had caused significant increase of ¹²⁹I levels in oyster (P < 0.001) and kelp (P < 0.05) from Dapeng Peninsula between Jun-2011 and Apr-2012. However, the ¹²⁹I levels in oyster and kelp were far below the guideline given by Codex Alimentarius Commission and would not cause immediate harm to the health of local residents.     

Input of 129I into the western Pacific Ocean resulting from the Fukushima nuclear event

We present an initial characterization of the input of ¹²⁹I into the Pacific Ocean resulting from the 2011 Fukushima nuclear accident. This characterization is based primarily on ¹²⁹I measurements on samples collected from a research cruise conducted in waters off the eastern coast of Japan in June 2011. These measurements were compared with samples intended to reflect pre-Fukushima background that were collected during a May 2011 transect of the Pacific by a commercial container vessel. In surface waters, we observed peak ¹²⁹I concentrations of ~300 μBq/m³ which represents an elevation of nearly three orders of magnitude compared to pre-Fukushima backgrounds. We coupled our ¹²⁹I results with ¹³⁷Cs measurements from the same cruise and derived an average ¹²⁹I/¹³⁷Cs activity ratio of 0.442 × 10^?6 for the effluent from Fukushima. Finally, we present ¹²⁹I depth profiles from five stations from this cruise which form the basis for future studies of ocean transport and mixing process as well as estimations of the total budget of ¹²⁹I released into the Pacific.     

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.     

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.     

The use of charcoal from agriculture waste in the speciation of iodine from well and river waters

The concentrations of iodine in fresh waters are known to be within the range of 0.5 to 35 ng·ml⁻¹, much lower than in oceanic waters. The iodine concentrations, particularly that of¹²⁹I which is significant from the radiation safety aspect, in public drinking waters have to be specified in order to verify the required level before distribution for domestic use. A modified version of an established method was used in the adsorption of iodine, iodate, total inorganic iodine and charcoal-adsorbable iodine using activated carbon prepared from oil palm kernel wastes. A thorough investigation of the physical properties of the activated carbon was carried out to determine its viability as an adsorbent for volatile species such as iodine. The iodine species were preconcentrated from water samples collected from wells in villages and from water intake points along rivers. The quantitative analysis of the species adsorbed was done by irradiating the activated charcoal loaded with the respective species in a neutron flux of 5.1·10¹² n·cm⁻²·s⁻¹ from a TRIGA MkII, nuclear reactor. Recovery experiments using spiked samples was done to provide quality assurance controls.     

Iodine-129 in Missouri rain and milk

A combination of neutron activation and mass spectrometry was used to measure¹²⁹I and¹²⁷I in local samples of rain and milk. The general distribution of values for the¹²⁹I/¹²⁷I ratio in these samples can be understood in terms of well established geochemical and biological cycles of iodine, but the origin of high¹²⁹I/¹²⁷I ratios in a few of the samples collected in 1976 is not understood. The procedures used to extract and purify iodine were tested by monitoring¹³¹I in rain and milk following the Chinese atmospheric bomb test of September 17, 1977.     

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.     

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.     

Determination of the loss of 129I from milk during storage using neutron activation analysis

¹²⁹I is a long-lived radionuclide (T_1/2 = 1.6. 10⁷ y) present in Sellafield aerial emissions which transfersthrough the air–grass–cow–milk pathway. Concentrations of ¹²⁹I in milk are regularly monitored and they are also predicted bymodeling, the results of which are used to set limits on the discharges fromSellafield. It has been suggested that the analysis may under-estimate theconcentration of ¹²⁹I in milk due to a loss of thisradioisotope during storage of the milk before analysis takes place. Thisstudy used neutron activation analysis to determine ¹²⁹I in a milksample obtained from a farm downwind of the Sellafield site, over a periodof ten weeks. Sub-samples of milk were removed from storage and analyzed after0, 3, 7, 14, 28, 49 and 70 days. A mean concentration of 4.4 mBq . l ^—1 was determined in the milk and analysis of the results showedthat there was no discernible loss of ¹²⁹I from the milk over the10-week storage period. The stable iodine content of the milk was also determinedand was found to be within the normal range quoted in the literatureof between 0.01 and 1 mg . l ^—1 .     

Seasonal variation of 129I species in the Baltic Proper

Iodine speciation plays a significant role in iodine volatilizing into atmosphere from the seas, as well as serving as a biological indicator. Despite this importance, the data on iodine species revealed inconclusive evidence of what factors controlling speciation transformation. We here present new data on profiles of ¹²⁹I speciation in the Baltic Proper during November 2009. Along with the two earlier investigations (August 2006 and April 2007), an assessment of seasonal variation of ¹²⁹I species is presented. The results show that, due to the anoxic nature of Baltic Proper, presence of ¹²⁹IO₃ ^? in the Baltic Proper does not follow an obvious seasonal cycle, as the case with ¹²⁹I^?. Concentrations of ¹²⁹I^? in the Baltic Proper exhibit higher values in summer than the other two seasons (spring and winter), which might be associated with degrading of organic matter and release from sediment to water column that is more pronounced during summer. ¹²⁹I^? in surface water from the three seasons does not reflect the release function from the reprocessing facilities during the period April 2007 to November 2009. Consequently variability of ¹²⁹I^? in surface seawater of the Baltic Proper depends, to some extent, on local physical as well as biochemical conditions.