Marine radioecology after the Fukushima Dai-ichi nuclear accident: Are we better positioned to understand the impact of radionuclides in marine ecosystems?

This paper focuses on how a community of researchers under the COMET (CO-ordination and iMplementation of a pan European projecT for radioecology) project has improved the capacity of marine radioecology to understand at the process level the behaviour of radionuclides in the marine environment, uptake by organisms and the resulting doses after the Fukushima Dai-ichi nuclear accident occurred in 2011. We present new radioecological understanding of the processes involved, such as the interaction of waterborne radionuclides with suspended particles and sediments or the biological uptake and turnover of radionuclides, which have been better quantified and mathematically described. We demonstrate that biokinetic models can better represent radionuclide transfer to biota in non-equilibrium situations, bringing more realism to predictions, especially when combining physical, chemical and biological interactions that occur in such an open and dynamic environment as the ocean. As a result, we are readier now than we were before the FDNPP accident in terms of having models that can be applied to dynamic situations. The paper concludes with our vision for marine radioecology as a fundamental research discipline and we present a strategy for our discipline at the European and international levels. The lessons learned are presented along with their possible applicability to assess/reduce the environmental consequences of future accidents to the marine environment and guidance for future research, as well as to assure the sustainability of marine radioecology. This guidance necessarily reflects on why and where further research funding is needed, signalling the way for future investigations.

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.

Dose assessment to workers in a dicalcium phosphate production plant.

The production of dicalcium phosphate (DCP) uses phosphate rock (PR) as a raw material. Sedimentary phosphate rocks are enriched with relevant concentrations of natural radionuclides from the 238U decay chain (around 103 Bq·kg-1), leading to the need of controlling potential exposures to radiation of workers and members of the public in accordance with IAEA safety standards. Indeed, phosphate industries are classified as Naturally Occurring Radioactive Material (NORM) industries. Thus, the aim of this work is to assess the radiological risk of the workers in a DCP production plant located in the Iberian Peninsula (South-West Europe), which digests PR with hydrochloric acid. In the present study 238U, 230Th, 222Rn, 210Pb and 210Po concentrations in aerosols (indoor and outdoor areas) are reported. Aerosols showed concentrations between 0.42-92 mBq·m-3 for 238U, 0.24-33 mBq·m-3 for 230Th, 0.67-147 mBq·m-3 for 210Pb and 0.09-34 mBq·m-3 for 210Po. Long-term exposure (four months) of passive 222Rn detectors provided concentrations that ranged from detection limit (< DL) to 121 Bq·m-3 in outdoor areas and from < DL to 211 Bq·m-3 in indoor areas, similar to concentrations obtained from short-term measurements with active detectors from < DL to 117 Bq·m-3 in outdoor areas and from < DL to 318 Bq·m-3 in indoor places. 226Ra accumulation in ebonite and pipe scales were the most important contributions to the ambient dose equivalent H*(10), resulting in 0.07 (background)-27 µSv·h-1 with a median value of 1.1 µSv·h-1. Average 222Rn air concentrations were lower than the 300 Bq·m-3 limit and therefore, according to European Directive 2013/59/EURATOM, 222Rn concentration is excluded from the worker operational annual effective dose. Thus, considering the inhalation of aerosols and the external dose sources, the total effective dose determined for plant operators was 0.37 mSv·y-1.

Influence of submarine groundwater discharge on (210)Po and (210)Pb bioaccumulation in fish tissues.

This study presents the results of the accumulation of (210)Po and (210)Pb in fish tissues and organs in a brackish-water marshland that is characterized by high concentrations of (222)Rn and (226)Ra supplied by submarine groundwater discharge (SGD). Tissues and organs from Cyprinus carpio, Chelon labrosus and Carassius auratus in the wetland were significantly enriched by both (210)Pb and (210)Po (up to 55 and 66 times, respectively) compared to blanks. The major input route of (210)Pb and (210)Po into the fish body seems to be through ingestion, due to the high levels of (210)Pb and (210)Po found in the gut content as well as in organs involved in digestion and metabolism (i.e. gut, kidney and hepatopancreas). Results showed that (210)Po was more accumulated in all fish tissues and organs except for the spine, which showed a higher affinity for (210)Pb, due to its capacity to replace Ca from apatite in bones. Over all the variables analyzed, fish tissues/organs and, secondarily, fish species were the most important factors explaining the concentration of radionuclides, whereas fish length and the sampling location played a minor role. The relationship of the two radionuclides varied markedly among tissues and their concentration levels were only correlated in gills, gut and, marginally, in spines. In general, the highest values of (210)Pb and (210)Po concentrations in tissues were found on C. labrosus tissues rather C. auratus and C. carpio. This study demonstrates that inputs of natural radionuclides supplied by SGD to coastal semi-enclosed areas (such as marshlands, lagoons or ponds) may significantly increase the contents of (210)Pb and (210)Po in fish tissues/organs. Thus, this study represents one of the first evidences of direct ecological effects derived from SGD.

Dispersion and fate of 9°Sr in the Northwestern Pacific and adjacent seas: global fallout and the Fukushima Dai-ichi accident.

The 3D compartment model POSEIDON-R was applied to the Northwestern Pacific and adjacent seas to simulate the transport and fate of (90)Sr in the period 1945-2010 and to perform a radiological assessment on the releases of (90)Sr due to the Fukushima Dai-ichi nuclear accident for the period 2011-2040. The contamination due to runoff of (90)Sr from terrestrial surfaces was taken into account using a generic predictive model. A dynamical food-chain model describes the transfer of (90)Sr to phytoplankton, zooplankton, molluscs, crustaceans, piscivorous and non-piscivorous fishes. Results of the simulations were compared with observation data on (90)Sr for the period 1955-2010 and the budget of (90)Sr activity was estimated. It was found that in the East China Sea and Yellow Sea the riverine influx was 1.5% of the ocean influx and it was important only locally. Calculated concentrations of (90)Sr in water, bottom sediment and marine organisms before and after the Fukushima Dai-ichi accident are in good agreement with available experimental measurements. The concentration of (90)Sr in seawater would return to the background levels within one year after leakages were stopped. The model predicts that the concentration of (90)Sr in fish after the Fukushima Dai-ichi accident shall return to the background concentrations only 2 years later due to the delay of the transfer throughout the food web and specific accumulation of (90)Sr. The contribution of (90)Sr to the maximal dose rate due to the FDNPP accident was three orders of magnitude less than that due to (137)Cs, and thus well below the maximum effective dose limits for the public.

Numerical modeling of the releases of (90)SR from Fukushima to the ocean: an evaluation of the source term.

A numerical model consisting of a 3D advection/diffusion equation, including uptake/release reactions between water and sediments described in a dynamic way, has been applied to simulate the marine releases of (90)Sr from the Fukushima power plant after the March 2011 tsunami. This is a relevant issue since (90)Sr releases are still occurring. The model used here had been successfully applied to simulate (137)Cs releases. Assuming that the temporal trend of (90)Sr releases was the same as for (137)Cs during the four months after the accident simulated here, the source term could be evaluated, resulting in a total release of 80 TBq of (90)Sr until the end of June, which is in the lower range of previous estimates. Computed vertical profiles of (90)Sr in the water column have been compared with measured ones. The (90)Sr inventories within the model domain have also been calculated for the water column and for bed sediments. Maximum dissolved inventory (obtained for April 10th, 2011) within the model domain results in about 58 TBq. Inventories in bed sediments are 3 orders of magnitude lower than in the water column due to the low reactivity of this radionuclide. (90)Sr/(137)Cs ratios in the ocean have also been calculated and compared with measured values, showing both spatial and temporal variations.

Determination of U and Th α-emitters in NORM samples through extraction chromatography by using new and recycled UTEVA resins.

This manuscript describes a protocol for the determination of U and Th isotopes via alpha spectrometry in NORM samples containing high concentrations of these radionuclides, up to kBq kg(-1). This technique is based on extraction chromatography with UTEVA (Triskem Int.) resins and it has been tested using both NORM samples from a phosphate industry and reference materials. The results proved that this method is highly optimized in terms of accuracy and precision when dealing with NORM samples. Recycling of UTEVA columns was also checked using NORM samples and successful results were obtained for both U and Th isotopes, thus proving the feasibility of re-using these type of columns.

Evaluation of different parameters affecting the liquid scintillation spectrometry measurement of gross alpha and beta index in water samples.

Liquid scintillation spectrometry is a fast competitive technique for the simultaneous evaluation of gross alpha and beta indexes. However, the implementation of this technique should not be considered as straightforward, and the pre-concentration methods to decrease the detection limit together with quenching and alpha, and beta crossover corrections should be carefully chosen according to the needs of the laboratory. Both aspects are being approached in this work as to find an easy and robust method for alpha/beta measurement in water samples, taking into account the quenching and alpha/beta crossover interferences effects. Results showed that most of the pre-concentration methods increased the quenching in the measurement, although HNO(3) 0.05 M points to be the best solution for pre-concentration and re-dissolution of the sample as converges into low quenching and maximum recovery. Subsequently, in the measurement of water samples with different conductivities, the analysis of the raw counts to obtain gross alpha and beta indexes was carried out using different approaches to implement quenching and interference corrections. If quenching and salt content in the sample are relatively low, interference and quenching-efficiency corrections do not improve the accuracy of the results within the usual precision assumed for a result of gross alpha and beta index (25%). Special attention must be paid when corrections are applied to high quenched or saline samples and when alpha and beta activities values are different in several orders of magnitude.

Fluxes of 238U decay series radionuclides in a dicalcium phosphate industrial plant.

The production of dicalcium phosphate (DCP) is part of the phosphate industry, which has been recently included in the positive list of the NORM industries defined in the revised version of the EU-BSS (Euratom 29/96). The objective of the present work is to study specific concentrations and fluxes of (238,234)U, (230)Th, (226)Ra, (210)Pb and (210)Po at the different stages of the DCP production. Results showed highest activities of (238)U and (210)Pb were found in DCP (1500-2000 Bq kg(-1)); (230)Th and (210)Po were released together with the sludges (1600-2000 Bq kg(-1)) and (226)Ra presented particularly high activities in water (48 × 10(3) Bq m(-3)) and in the reactor scales (115 × 10(3) Bq kg(-1)). Fluxes of radionuclides showed that (238)U outflows were equally distributed between sludges (16 × 10(3) kBq h(-1)) and dicalcium phosphate (20 × 10(3) kBq h(-1)); (230)Th and (210)Po were almost entirely released in the sludges (30 × 10(3)kBq h(-1)) and the greatest (210)Pb outflow was the DCP current (25 × 10(3) kBq h(-1)). (226)Ra was mainly discharged through the water effluent (12 × 10(3) kBq h(-1)). This work highlights the importance of studying the industrial processes involving NORM, as minor changes in the production steps lead to different radionuclide distribution in the process.

Distribution and biokinetic analysis of 210Pb and 210Po in poultry due to ingestion of dicalcium phosphate.

Dicalcium phosphate (DCP) is used as a calcium supplement for food producing animals (i.e., cattle, poultry and pig). When DCP is produced via wet acid digestion of the phosphate rock and depending on the acid used in the industrial process, the final product can result in enhanced (210)Pb and (210)Po specific activities (approximately 2000 Bq.kg(-1)). Both (210)Pb and (210)Po are of great interest because their contribution to the dose received by ingestion is potentially large. The aims of this work are to examine the accumulation of (210)Pb and (210)Po in chicken tissues during the first 42 days of life and to build a suitable single-compartment biokinetic model to understand the behavior of both radionuclides within the entire animal using the experimental results. Three commercial corn-soybean-based diets containing different amounts and sources of DCP were fed to broilers during a period of 42 days. The results show that diets containing enhanced concentrations of (210)Pb and (210)Po lead to larger specific accumulation in broiler tissues compared to the blank diet. Radionuclides do not accumulate homogeneously within the animal body: (210)Pb follows the calcium pathways to some extent and accumulates largely in bones, while (210)Po accumulates to a large extent in liver and kidneys. However, the total amount of radionuclide accumulation in tissues is small compared to the amounts excreted in feces. The single-compartment non-linear biokinetic model proposed here for (210)Pb and (210)Po in the whole animal takes into account the size evolution and is self-consistent in that no fitting parameterization of intake and excretions rates is required.

Radioactivity contents in dicalcium phosphate and the potential radiological risk to human populations.

Potentially harmful phosphate-based products derived from the wet acid digestion of phosphate rock represent one of the most serious problems facing the phosphate industry. This is particularly true for dicalcium phosphate (DCP), a food additive produced from either sulphuric acid or hydrochloric acid digestion of raw rock material. This study determined the natural occurring radionuclide concentrations of 12 DCP samples and 4 tricalcium phosphate (TCP) samples used for animal and human consumption, respectively. Metal concentrations (Al, Fe, Zn, Cd, Cr, As, Hg, Pb and Mg) were also determined. Samples were grouped into three different clusters (A, B, C) based on their radionuclide content. Whereas group A is characterized by high activities of 238U, 234U (approximately 10(3) Bq kg(-1)), 210Pb (2 x 10(3) Bq kg(-1)) and (210)Po ( approximately 800 Bq kg(-1)); group B presents high activities of (238)U, (234)U and (230)Th (approximately 10(3) Bq kg(-1)). Group C was characterized by very low activities of all radionuclides (< 50 Bq kg(-1)). Differences between the two groups of DCP samples for animal consumption (groups A and B) were related to the wet acid digestion method used, with group A samples produced from hydrochloric acid digestion, and group B samples produced using sulphuric acid. Group C includes more purified samples required for human consumption. High radionuclide concentrations in some DCP samples (reaching 2 x 10(3) and 10(3) Bq kg(-1) of 210Pb and 210Po, respectively) may be of concern due to direct or indirect radiological exposure via ingestion. Our experimental results based on 210Pb and 210Po within poultry consumed by humans, suggest that the maximum radiological doses are 11 +/- 2 microSv y(-1). While these results suggest that human health risks are small, additional testing should be conducted.