Anthropogenic 236U and 129I in the Mediterranean Sea: First comprehensive distribution and constrain of their sources.

The first basin-wide distribution of 236U/238U atom ratios and 129I concentrations is presented for the Mediterranean Sea. During the GEOTRACES GA04S-MedSeA expedition in 2013 seawater was collected from 10 vertical profiles covering the principal sub-basins of the Mediterranean Sea. The main objective was to understand the distributions of 236U and 129I in relation to the water masses, and to constrain their sources in this region. The 236U/238U atom ratios and the 129I concentrations ranged from (710±40)×10-12 to (2220±60)×10-12 and from (4.0±0.1)×107 to (13.8±0.3)×107at·kg-1, respectively. The results show that radionuclide-poor Atlantic Water is entering at the surface through the Strait of Gibraltar whereas comparably radionuclide-enriched Levantine Intermediate Water is sinking in the Eastern Basin and flowing westward at intermediate depths. Low radionuclide levels were found in the oldest water masses at about 1000-2000m depth in the Eastern Basin. At greater depths, waters were relatively enriched in 236U and 129I due to dense water formation occurring in both, the Eastern and Western Basins. The inventories of 236U and 129I cannot be explained only by global fallout from atmospheric nuclear bomb testings carried out in the 1950s and 1960s. We estimate that the liquid input of 236U from the nuclear reprocessing facility of Marcoule (France), via the Rhône river, was of the same order of magnitude than the contribution from global fallout, whereas liquid and gaseous releases of 129I from Marcoule were up to two orders of magnitude higher than global fallout. For both radionuclides, the contribution from the Chernobyl accident is found to be minor.

Iodine-129, Iodine-127 and Cesium-137 in seawater from the North Sea and the Baltic Sea.

In this study, new data are presented for the iodine isotopes (127I, 129I and their isotopic ratios) and Cesium (137Cs) in water samples of the North Sea and the Baltic Sea in 2005 and 2009. This study supplements and extends the study of Michel et al. (2012). Iodine isotopes were separated from their matrix by using an anion exchange method and were determined by applying ICP-MS and AMS. 137Cs in seawater was determined after cesium ion exchange procedure enrichment by gamma-spectrometry. The concentrations of 127I in seawater of the North and Baltic Sea are fairly constant in each Sea with averages of (44 ± 2) and (21 ± 1) ng g-1, respectively, depending on the salinity. However, large variations of 129I concentrations in these areas were detected, which decreased along the French, Belgian, Dutch, German, and Danish shores. 129I/127I isotope ratios in the Baltic Sea are about 10 times lower than in the North Sea in 2009. The highest isotopic ratios (2.7 × 10-6) was detected in the English Channel east of the nuclear reprocessing plant at Cap de la Hague. The results confirm the result of our early study that the sources of 129I in the North Sea are primarily the nuclear reprocessing facilities at Sellafield (UK) and La Hague (F), and that in the Baltic Sea the inflow of water from North Sea through the Danish Straits dominates the occurrence of 129I. In 2009, the activity concentration of 137Cs was at least 6 times higher in the Baltic Sea (37 Bq m-3) than in the North Sea (5.9 Bq m-3), due to release of 137Cs from sediments in the Baltic Sea, which were contaminated by the Chernobyl accident and - to a minor degree - the atmospheric explosions of atomic bombs. The results are discussed by comparing the results of our previous work and the current study demonstrating the continuing disequilibrium of 129I/127I atomic ratio in the environmental compartments.

Concentrations of iodine isotopes ((129)I and (127)I) and their isotopic ratios in aerosol samples from Northern Germany.

New data about (129)I, (127)I concentrations and their isotopic ratios in aerosol samples from the trace survey station of the Physikalisch-Technische Bundesanstalt (PTB) in Braunschweig, Northern Germany, are presented and discussed in this paper. The investigated samples were collected on a weekly basis during the years 2011 to 2013. Iodine was extracted from aerosol filters using a strong basic solution and was separated from the matrix elements with chloroform and was analysed by accelerator mass spectrometry (AMS) for (129)I and by inductively coupled plasma mass spectrometry (ICP-MS) for (127)I. The concentrations of (127)I and (129)I in aerosol filters ranged from 0.31 to 3.71 ng m(-3) and from 0.06 to 0.75 fg m(-3), respectively. The results of (129)I/(127)I isotopic ratios were in the order 10(-8) to 10(-7). The (129)I originated directly from gaseous emissions and indirectly from liquid emissions (via sea spray) from the reprocessing plants in Sellafield and La Hague. In comparison with the results of (131)I after the Fukushima accident, no contribution of (129)I from this accident was detectable in Central Europe due to the high background originating from the (129)I releases of the European reprocessing plants. (129)I atmospheric activity concentrations were compared with those of an anthropogenic radionuclide ((85)Kr). We did not find any correlation between (129)I and (85)Kr, both having nuclear reprocessing plant as the main source.

Retrospective dosimetry of Iodine-131 exposures using Iodine-129 and Caesium-137 inventories in soils--A critical evaluation of the consequences of the Chernobyl accident in parts of Northern Ukraine.

The radiation exposure of thyroid glands due to (131)I as a consequence of the Chernobyl accident was investigated retrospectively based on (129)I and (137)Cs inventories in soils in Northern Ukraine. To this end, soil samples from 60 settlements were investigated for (129)I, (127)I, and (137)Cs by AMS, ICP-MS and gamma-spectrometry, respectively. Sampling was performed between 2004 und 2007. In those parts of Northern Ukraine investigated here the (129)I and (137)Cs inventories are well correlated, the variability of the individual (129)I/(137)Cs ratios being, however, high. Both the (129)I and (137)Cs inventories in the individual 5 samples for each settlement allowed estimating the uncertainties of the inventories due to the variability of the radionuclide deposition and consequently of the retrospective dosimetry. Thyroid equivalent doses were calculated from the (129)I and the (137)Cs inventories using aggregated dose coefficients for 5-year old and 10-year-old children as well as for adults. The highest thyroid equivalent doses (calculated from (129)I inventories) were calculated for Wladimirowka with 30 Gy for 5-years-old children and 7 Gy for adults. In 35 settlements of contamination zone II the geometric mean of the thyroid equivalent doses was 2.0 Gy for 5-years-old children with a geometric standard deviation (GSD) of 3.0. For adults the geometric mean was 0.47 Gy also with a GSD of 3.0. In more than 25 settlements of contamination zone III the geometric means were 0.82 Gy for 5-years old children with a GSD of 1.8 and 0.21 Gy for adults (GSD 1.8). For 45 settlements, the results of the retrospective dosimetry could be compared with thyroid equivalent doses calculated using time-integrated (131)I activities of thyroids which were measured in 1986. Thus, a critical evaluation of the results was possible which demonstrated the general feasibility of the method, but also the associated uncertainties and limitations.

Iodine-129, iodine-127 and caesium-137 in the environment: soils from Germany and Chile.

Soil profiles from Bavaria in southern Germany and from Chile were analysed for (129)I by accelerator mass spectrometry (AMS), for (127)I by inductively coupled plasma mass spectrometry (ICP-MS), and for (137)Cs by gamma-spectrometry. The mean deposition density of (137)Cs in soils from Bavaria was (41×1.5(±1)) kBq m(-2) (geometric mean and geometric standard deviation), originating mostly from the Chernobyl fall-out. The deposition density of (129)I in these soils was (109×1.5(±1)) mBq m(-2). The dominant sources of (129)I in Bavaria are, however, the reprocessing plants La Hague and Sellafield and not the Chernobyl fall-out. The (129)I/(127)I isotopic ratios of the Bavarian soils were between 10(-7) and 10(-10), i.e. 10(2)-10(5) times higher than the ratios observed for the samples from Chile. The (129)I integral deposition densities in Chile, Easter Island and Antarctica were between 0.3 mBq m(-2) and 2 mBq m(-2). In these soils, the observed (129)I/(127)I ratios were about 10(-12). The soils from Chile allow the determination of the (129)I fall-out from the atmospheric nuclear weapons explosions undisturbed from contaminations due to releases from reprocessing plants. An upper limit of the integral (129)I deposition density of the atmospheric nuclear weapons explosions on the Southern Hemisphere (27°S) is about 1 mBq m(-2). Finally, the dependence of the migration behaviour of (137)Cs, (127)I and of (129)I on the soil properties is discussed. It turns out that there is a distinctly different behaviour of (127)I, (129)I, and (137)Cs in the soils exhibiting different sorption mechanisms for old and recent iodine as well as for (137)Cs.

Iodine-129 and iodine-127 in European seawaters and in precipitation from Northern Germany.

In order to obtain a comprehensive survey on the consequences of the marine (129)I discharges from the European reprocessing plants La Hague and Sellafield, the distribution of (129)I and (127)I in surface waters of the North Sea, the English Channel, the Irish Sea, and the Northeast Atlantic was studied using accelerator mass spectrometry for (129)I and ICP-MS for (127)I. Samples of seawater were taken in the German Bight in May, September, and November 2005 and in the entire North Sea and the English Channel in August 2005. Further samples were obtained from the Irish Sea in June and August 2006 and from Arctic waters between Spitsbergen and Southern Norway in September 2005. (129)I is a conservative tracer in seawater. The concentrations of (127)I are relatively constant with exceptions of coastal areas with high biological activity and of areas influenced by influx from rivers and the Baltic Sea. The variability of the (129)I/(127)I isotopic ratios is exclusively determined by admixture of (129)I released from the reprocessing facilities Sellafield and La Hague to the seawater. The (129)I/(127)I ratios were between 4 × 10(-9)and 3 × 10(-6): at least 3 orders of magnitude higher than the natural equilibrium isotopic ratio 1.5 × 10(-12). (129)I/(127)I ratios of a few times 10(-10) were only found in seawater from the Indian Ocean and from the Pacific at Hawaii. Comparison of the results obtained for seawater with those of a measurement of airborne iodine species and with iodine isotopes in precipitation in Northern Germany demonstrates the transfer of (129)I and (127)I from the sea into the atmosphere and the dominating role of the marine discharges for the atmospheric fallout of (129)I in Western Europe. The results are discussed with the goal to estimate the relevance of the marine discharges for the contamination of the continental areas.

Determination of 129I/127I in aerosol samples in Seville (Spain).

In this work we present results of the (129)I/(127)I ratio in aerosols of Seville, Southwest of Spain (37.4 degrees N,6 degrees W). A radiochemical method is applied to extract the iodine from the aerosols and prepare samples to be measured by accelerator mass spectrometry (AMS) at the ETH facility in Zürich. We have found the possibility of monitoring the (129)I/(127)I isotopic ratio on a two-days basis with sensitivities in the order of 10(4)-10(5) atoms (129)I/m(3), and values of 10(-8)-10(-9) for the isotopic ratio.

Iodine-129 in soils from Northern Ukraine and the retrospective dosimetry of the iodine-131 exposure after the Chernobyl accident.

Forty-eight soil profiles down to a depth of 40 cm were taken in Russia and Ukraine in 1995 and 1997, respectively, in order to investigate the feasibility of retrospective dosimetry of the 131I exposure after the Chernobyl accident via the long-lived 129I. The sampling sites covered areas almost not affected by fallout from the Chernobyl accident such as Moscow/Russia and the Zhitomir district in Ukraine as well as the highly contaminated Korosten and Narodici districts in Ukraine. 129I was analyzed by radiochemical neutron activation analysis (RNAA) and accelerator mass spectrometry (AMS). 127I was measured for some profiles by RNAA or ion chromatography (IC). The results for 127I demonstrated large differences in the capabilities of the soils to store iodine over long time spans. The depth profiles of 129I and of 137Cs showed large differences in the migration behavior between the two nuclides but also for each nuclide among the different sampling sites. Though it cannot be quantified how much 129I and 137Cs was lost out of the soil columns into deeper depths, the inventories in the columns were taken as proxies for the total inventories. For 129I, these inventories were at least three orders of magnitude higher than a pre-nuclear value of 0.084+/-0.017 mBq m(-2) derived from a soil profile taken in 1939 in Lutovinovo/Russia. From the samples from Moscow and Zhitomir, a pre-Chernobyl 129I inventory of (44+/-24) mBq m(-2) was determined, limiting the feasibility of 129I retrospective dosimetry to areas where the 129I inventories exceed 100 mBq m(-2). Higher average 129I inventories in the Korosten and Narodici districts of 130 and 848 mBq m(-2), respectively, allowed determination of the 129I fallout due to the Chernobyl accident. Based on the total 129I inventories and on literature data for the atomic ratio of 129I/131I=13.6+/-2.8 for the Chernobyl emissions and on aggregated dose coefficients for 131I, the thyroid exposure due to 131I after the Chernobyl accident was estimated for the inhabitants of four villages in the Korosten and of three villages in the Narodici districts. The limitations and uncertainties of the 129I retrospective dosimetry are discussed.

Relative influence of 129I sources in a sediment core from the Kattegat area.

The depth profiles of the (129)I concentration and the (129)I/(127)I ratio in a surface sediment core from the Kattegat area have been analyzed in order to obtain information about the different sources of (129)I in that core. Therefore, a mathematical model that relates the measured values to the available emission data from the nuclear fuel reprocessing plants and nuclear weapons tests has been applied. Results show that the reprocessing plants at La Hague and Sellafield are the main sources of (129)I in the sediment. Results about the transfer from the release points at the reprocessing plants to the sampling zone agree with other literature data. The model calculates quite fast the sedimentation of (129)I in the sampling place, probably attached to organic matter. Finally, an estimation of approximately 89 kg of (129)I released by Sellafield between 1952 and 1968 has been obtained from the model.

Wet and dry deposition of 129I in Seville (Spain) measured by accelerator mass spectrometry.

Iodine-129 (T1/2 = 1.57 x 10(7) yr) concentrations have been determined by accelerator mass spectrometry in rainwater samples taken at Seville (southwestern Spain) in 1996 and 1997. This technique allows a reduction in the detection limits for this radionuclide in comparison to radiometric counting and other mass spectrometric methods such as ICP-MS. Typical 129I concentrations range from 4.7 x 10(7) 129I atoms/l (19.2%) to 4.97 x 10(9) 129I atoms/l (5.9%), while 129I depositions are normally in the order of 10(8)-10(10) atoms/m2d. These values agree well with other results obtained for recent rainwater samples collected in Europe. Apart from these, the relationship between 129I deposition and some atmospheric factors has been analyzed, showing the importance of the precipitation rate and the concentration of suspended matter in it.

Determination of 129I in atmospheric samples by accelerator mass spectrometry.

A method for the radiochemical extraction of 129I from atmospheric charcoal filters and its measurement by accelerator mass spectrometry is presented. Either the 129I concentration or the 129I/127I atom ratio can be determined in the sample. With this method, air filters from Seville, in the Southwest of Spain (37.4 degrees N, 6 degrees W) have been analyzed. Sensitivities in the order of 10(4) atoms/m3 for 129I concentrations and 10(-10) for 129I/127I atom ratios are obtained. AMS measurements are performed with the 6 MV tandem accelerator at the ETH-Hönggerberg in Zurich.

On the analysis of iodine-129 and iodine-127 in environmental materials by accelerator mass spectrometry and ion chromatography.

Based on a review of literature about the abundances of 129I (T1/2 = 15.7 Ma) in the environment we show that there is a severe lack of knowledge, in particular about natural, pre-nuclear levels. Among the two analytical techniques which are sensitive enough to investigate 129I in environmental materials, namely radiochemical neutron activation analysis (RNAA) and accelerator mass spectrometry (AMS), only AMS is capable of covering the natural, pre-nuclear levels. Since such AMS measurements require chemical separation of iodine from the matrix, a wide variety of separation schemes are necessary for environmental analyses. We report here on such schemes for the analysis of soils, plants and soft tissue. They are applied exemplarily to analyses of soils from the vicinity of Chernobyl. For chemical separations prior to analysis, contamination control and blank analyses are essential. Here, we discuss quality control procedures in detail, both for RNAA and AMS. In the case of AMS we use ion-chromatography (IC) for the determination of stable iodine. The IC analysis is included in the separation schemes for environmental materials. First AMS-analyses of terrestrial biospheric materials demonstrate that natural environmental levels of 129I are lower than previously deduced from investigations using RNAA, but higher than expected from model calculations. AMS is capable of providing the missing knowledge about the radioecology of 129I.