A new certified reference material IAEA-465 for radionuclides in Baltic Sea sediment.

Certified reference material (CRM) for natural (40K,210Pb,210Po,226Ra,228Ra,228Th,230Th,232Th,234U,235U, and238U) and anthropogenic (137Cs,239+240Pu, and241Am) radionuclides in marine sediment from the Baltic Sea (IAEA-465) has been developed. Information values are given for 238Pu,239Pu and240Pu. Altogether 27 laboratories participated in this exercise. Radiometric (alpha-spectrometry, gamma-spectrometry and beta counting, as well as mass spectrometry (ICP-MS and AMS) techniques were applied in measurements. The CRM is intended to be used for Quality Assurance/Quality Control of radionuclide analyses, for the development and validation of analytical methods, for the development of reference methods and for training purposes.

Impact of Saharan dust events on radionuclides in the atmosphere, seawater, and sediments of the northwest Mediterranean Sea.

In February 2004, anthropogenic radionuclides (137Cs, 236U, 239Pu and 240Pu), transported from the Sahara Desert, were observed in the Monaco air, and later in water and sediment samples collected at the DYFAMED site in the northwest (NW) Mediterranean Sea. While 236U and 137Cs in Saharan dust particles showed a high solubility in seawater, Pu isotopes were particle reactive in the water column and in the sediment. The impact of the Saharan deposition was found at 0-1.0 cm of the sediment core for 236U and 137Cs, and between 1.0 and 1.5 cm for Pu isotopes. The excess of 236U was observed more in the water column than in the sediment, whereas the 239+240Pu total inventories were comparable in the water column and the sediment. This single-day particle event represented 72% of annual atmospheric deposition in Monaco. At the DYFAMED site, it accounted for 10% (137Cs) and 15% (239+240Pu) activities of sinking particles during the period of the highest mass flux collected at the 200 and 1000 m water depths, and for a significant proportion of the total annual atmospheric input to the NW Mediterranean Sea (28-37% for 137Cs and 34-45% for 239+240Pu). Contributions to the total 137Cs and 239+240Pu sediment inventories were estimated to be 14% and 8%, respectively. The Saharan dust deposition phenomenon (atmospheric input, water column and sediment) offered a unique case to study origin and accumulation rates of radionuclides in the NW Mediterranean Sea.

Impact of the Fukushima accident on tritium, radiocarbon and radiocesium levels in seawater of the western North Pacific Ocean: A comparison with pre-Fukushima situation.

Tritium, radiocarbon and radiocesium concentrations in water column samples in coastal waters offshore Fukushima and in the western North Pacific Ocean collected in 2011-2012 during the Ka'imikai-o-Kanaloa (KoK) cruise are compared with other published results. The highest levels in surface seawater were observed for 134Cs and 137Cs in seawater samples collected offshore Fukushima (up to 1.1 Bq L-1), which represent an increase by about three orders of magnitude when compared with the pre-Fukushima concentration. Tritium levels were much lower (up to 0.15 Bq L-1), representing an increase by about a factor of 6. The impact on the radiocarbon distribution was measurable, but the observed levels were only by about 9% above the global fallout background. The 137Cs (and similarly 134Cs) inventory in the water column of the investigated western North Pacific region was (2.7 ± 0.4) PBq, while for 3H it was only (0.3 ± 0.2) PBq. Direct releases of highly contaminated water from the damaged Fukushima NPP, as well as dry and wet depositions of these radionuclides over the western North Pacific considerably changed their distribution patterns in seawater. Presently we can distinguish Fukushima labeled waters from global fallout background thanks to short-lived 134Cs. However, in the long-term perspective when 134Cs will decay, new distribution patterns of 3H, 14C and 137Cs in the Pacific Ocean should be established for future oceanographic and climate change studies in the Pacific Ocean.

Excess of (236)U in the northwest Mediterranean Sea.

In this work, we present first (236)U results in the northwestern Mediterranean. (236)U is studied in a seawater column sampled at DYFAMED (Dynamics of Atmospheric Fluxes in the Mediterranean Sea) station (Ligurian Sea, 43°25'N, 07°52'E). The obtained (236)U/(238)U atom ratios in the dissolved phase, ranging from about 2×10(-9) at 100m depth to about 1.5×10(-9) at 2350m depth, indicate that anthropogenic (236)U dominates the whole seawater column. The corresponding deep-water column inventory (12.6ng/m(2) or 32.1×10(12) atoms/m(2)) exceeds by a factor of 2.5 the expected one for global fallout at similar latitudes (5ng/m(2) or 13×10(12) atoms/m(2)), evidencing the influence of local or regional (236)U sources in the western Mediterranean basin. On the other hand, the input of (236)U associated to Saharan dust outbreaks is evaluated. An additional (236)U annual deposition of about 0.2pg/m(2) based on the study of atmospheric particles collected in Monaco during different Saharan dust intrusions is estimated. The obtained results in the corresponding suspended solids collected at DYFAMED station indicate that about 64% of that (236)U stays in solution in seawater. Overall, this source accounts for about 0.1% of the (236)U inventory excess observed at DYFAMED station. The influence of the so-called Chernobyl fallout and the radioactive effluents produced by the different nuclear installations allocated to the Mediterranean basin, might explain the inventory gap, however, further studies are necessary to come to a conclusion about its origin.

Certified reference materials for radionuclides in Bikini Atoll sediment (IAEA-410) and Pacific Ocean sediment (IAEA-412).

The preparation and characterization of certified reference materials (CRMs) for radionuclide content in sediments collected offshore of Bikini Atoll (IAEA-410) and in the open northwest Pacific Ocean (IAEA-412) are described and the results of the certification process are presented. The certified radionuclides include: (40)K, (210)Pb ((210)Po), (226)Ra, (228)Ra, (228)Th, (232)Th, (234)U, (238)U, (239)Pu, (239+240)Pu and (241)Am for IAEA-410 and (40)K, (137)Cs, (210)Pb ((210)Po), (226)Ra, (228)Ra, (228)Th, (232)Th, (235)U, (238)U, (239)Pu, (240)Pu and (239+240)Pu for IAEA-412. The CRMs can be used for quality assurance and quality control purposes in the analysis of radionuclides in sediments, for development and validation of analytical methods and for staff training.

Certified Reference Material IAEA-446 for radionuclides in Baltic Sea seaweed.

A Certified Reference Material (CRM) for radionuclides in seaweed (Fucus vesiculosus) from the Baltic Sea (IAEA-446) is described and the results of the certification process are presented. The (40)K, (137)Cs, (234)U and (239+240)Pu radionuclides were certified for this material, and information values for 12 other radionuclides ((90)Sr, (99)Tc, (210)Pb ((210)Po), (226)Ra, (228)Ra, (228)Th, (230)Th, (232)Th, (235)U, (238)U, (239)Pu and (240)Pu) are presented. The CRM can be used for Quality Assurance/Quality Control of analysis of radionuclides in seaweed and other biota samples, as well as for development and validation of analytical methods, and for training purposes.

Detection of Fukushima Daiichi nuclear power plant accident radioactive traces in Monaco.

Daily air monitoring of radionuclides in the Principality of Monaco (43°73'N, 7°43'E) after the Fukushima Daiichi nuclear power plant accident showed that only Iodine-131 ((131)I) and Caesium isotopes ((134)Cs and (137)Cs) were detected. The peak of (131)I varied and reached its maximum between March 29th and April 5th, meanwhile both peaks of (134)Cs and (137)Cs arrived later and attained a maximum between April 1st and 4th. Their maximum activity concentrations in air were 354, 30, and 37 µBq m(-3) respectively. The (134)Cs to (137)Cs activity ratio was close to 1, which is different from that one observed after the Chernobyl accident (around 0.54). Up to 95% of caesium isotopes were washed out by wet scavenging during 27-28th of March, where the maximum deposition rates of (134)Cs and (137)Cs (13.7 and 19.1 mBq m(-2) day(-1), respectively) were observed. The significant input of (134)Cs and (137)Cs into the Mediterranean seawater column (30 m depth) was detected later, on the 24th of May. Radioisotopes of caesium and iodine were found far above the applied detection limits, but still with no concern for harmful radiation exposure and public health. The contamination gradually decreased in air and activity concentrations returned to background values after one or two months.

A new Certified Reference Material for radionuclides in Irish sea sediment (IAEA-385).

A new Certified Reference Material (CRM) for radionuclides in sediment (IAEA-385) is described and the results of the certification process are presented. Eleven radionuclides ((40)K, (137)Cs, (226)Ra, (228)Ra, (230)Th, (232)Th, (234)U, (238)U, (238)Pu, (239+240)Pu and (241)Am) have been certified and information mass activities with 95% confidence intervals are given for seven other radionuclides ((90)Sr, (210)Pb((210)Po), (235)U, (239)Pu, (240)Pu and (241)Pu). Results for less frequently reported radionuclides ((60)Co, (99)Tc, (134)Cs, (155)Eu, (224)Ra and (239)Np) and information on some activity and mass ratios are also reported. The CRM can be used for quality assurance/quality control of the analysis of radionuclides in sediment samples, for the development and validation of analytical methods and for training purposes.

IAEA programme on the quality of marine radioactivity data.

Society's growing interest in environmental issues requires the production of reliable information for policy-makers, stakeholders and society in general. This information must be based on accurate data produced by qualified laboratories and data need to be comparable between numerous laboratories for joint assessments, e.g. in International Conventions. The Marine Environment Laboratories of the International Atomic Energy Agency has been providing Quality Assurance services to laboratories involved in marine radioactivity studies for the past 30 years. This has included training, organization of laboratory intercomparison exercises, production of Reference Materials (RMs) and more recently, production of Certified Reference Materials (CRMs) that comply with relevant ISO standards. Here, the overall process of Certification of Reference Materials is reviewed, past work summarized and future needs of marine radioactivity laboratories briefly discussed.

Certified reference material for radionuclides in fish flesh sample IAEA-414 (mixed fish from the Irish Sea and North Sea).

A certified reference material (CRM) for radionuclides in fish sample IAEA-414 (mixed fish from the Irish Sea and North Seas) is described and the results of the certification process are presented. Nine radionuclides (40K, 137Cs, 232Th, 234U, 235U, 238U, 238Pu, 239+240Pu and 241Am) were certified for this material. Information on massic activities with 95% confidence intervals is given for six other radionuclides (90Sr, 210Pb(210Po), 226Ra, 239Pu, 240Pu 241Pu). Less frequently reported radionuclides (99Tc, 129I, 228Th, 230Th and 237Np) and information on some activity and mass ratios are also included. The CRM can be used for quality assurance/quality control of the analysis of radionuclides in fish sample, for the development and validation of analytical methods and for training purposes. The material is available from IAEA, Vienna, in 100 g units.

Characterization of the NIST seaweed Standard Reference Material.

The National Institute of Standards and Technology (NIST) Standard Reference Material (SRM) for seaweed was developed through an interlaboratory comparison with 24 participants from 16 countries. After evaluating different techniques to calculate certified values for the radionuclides, the median method was found to be the most representative technique. The certified values were provided for 13 radionuclides and information values were given for 15 more radionuclides. Results for the natural decay series showed disequilibrium in both the uranium and thorium series.

Kinetics of the adsorption and desorption of radionuclides of Co, Mn, Cs, Fe, Ag and Cd in freshwater systems: experimental and modelling approaches.

The sorption and release kinetics of 54Mn, 58Co, 59Fe, 109Cd, 110mAg and 134Cs by freshwater suspended particles were investigated to better identify the biogeochemical processes involved and to obtain suitable data for improving models describing radionuclide migration in freshwater streams. In order to observe any seasonal variability in the interaction of radionuclides with natural particles, experiments were performed both in winter and in summer during a phytoplanktonic bloom. Two kinetic models are compared in this paper: the "one-step reversible" model, based on the hypothesis that the transfer of radionuclides between water and suspended solids is governed by a reversible reaction, and the "two-successive-step reversible" model, which assumes two distinct types of sites or reactions on the solid phase. The "one-step reversible" model is generally unable to describe properly the exchange kinetics; this result shows that at least two processes are generally involved in radionuclide exchange between water and suspended particles. On the contrary, a model involving the existence of two successive reversible reactions properly simultes both the sorption and release kinetics. The determination of the kinetic coefficients allows quantitative assessment of the relative importance and kinetics of the processes. In particular, it has been shown that, except for Cs and Cd, major fractions of the radionuclides are associated at equilibrium with particulate sites involving strong interactions. The kinetics to reach this equilibrium depend on seasonal conditions, especially for Co and Mn: the transfer of Co and Mn to particulate sites involving strong interactions is much slower in winter. The distribution of the radionuclides between water and particulate sites involving weak interactions also shows seasonal variations for Co, Mn, Fe and Ag: the capacity to associate radionuclides is much higher in summer for Co and Mn, while the inverse tendency is observed for Fe and Ag. For Cs and Cd, no significant seasonal differences were observed.

Radionuclide concentrations in underground waters of Mururoa and Fangataufa Atolls.

In 1997 an expedition to Mururoa and Fangataufa Atolls was carried out to sample underground waters from cavity-chimneys and carbonate monitoring wells. The aim of this study was to determine the prevailing concentration and distribution status of radionuclides. Elemental analysis of interstitial waters was carried out in the water fraction as well as in particles collected at 11 underground monitoring wells. 238Pu, 239,240Pu, 241Am, 137Cs, 90Sr, 3H, 125Sb, 155Eu and 60Co were analyzed in both fractions by alpha-, beta- and gamma-spectrometry. Measurements showed that at 60% of the sites, pH and Eh seemed to be related to tidal cycles; in contrast HTO was constant during the sampling time. Interstitial waters from carbonates and transition zones shared similar chemical composition that were not different from that of the surrounding seawater. Waters collected from basalt cavities left after nuclear tests, (Aristee and Ceto) have a different chemical signature characterized by a deficiency in Mg, K and SO4 as well as enrichment in Sr, Si, Al and Cl compared to the rest of the stations. Radionuclide concentrations present in both, water and particulate fractions, were significantly higher at Ceto and Aristee than at any other monitoring wells, except for Fuseau and Mitre monitoring wells (Fangataufa) where values similar to Ceto were found (e.g. 239,240Pu: > 20 mBq g-1). Considering that Pu isotopes showed high Kd values compared to non-sorbing radionuclides such as 3H, 90Sr and 137Cs it is very unlikely that migration from cavities to monitoring wells accounts for the concentration of Pu isotopes and Am at Fuseau 30 and Mitre 27. Perhaps the contact of lagoon waters with the well before sealing could be a possible source of the transuranics found at these sites. The 238Pu/239,240Pu ratios measured in the particles were similar to that of the lagoon (0.38), thus supporting this hypothesis. The fact that transuranics were found only in the particle fraction, in the water (colloids included) these radionuclides were below detection limits, may be accounted for the conspicuous quantity of iron oxy-hydroxides present in the particulate fraction that under the appropriate redox conditions may be interacting selectively with elements in solution (scavenging) resulting in the enhanced transuranic signal. While transuranics have been found in places of their origin, radionuclides with low Kd values (3H, 90Sr, 137Cs) have already been transported to monitoring wells, as well as to the atolls' lagoons and the open ocean.