Reaching environmental levels of 244Pu by accelerator mass spectrometry at the Centro Nacional de Aceleradores.

244Pu (T1/2 = 81 My) is the longest-lived, most minor, and the most understudied Pu isotope. The anthropogenic production of 244Pu is linked to nuclear detonations. Reported 244Pu/239Pu atom ratios in environmental samples range from below 10-6 to above 10-3. This work discusses the performance of the 1 MV Accelerator Mass Spectrometry system at the Centro Nacional de Aceleradores (CNA, Seville, Spain) to analyse 244Pu at environmental levels. The presence of 232Th traces in the Pu sample limits the sensitivity of the technique through the formation of the diatomic trication (232Th12C)3+, of mass 244 u, which must be suppressed by adjusting the stripper gas pressure. A244Pu background of 0.0075 fg (2 × 104 at) is demonstrated for samples that have undergone a chemical treatment. The reliability of the technique is proved through the analysis of three reference sediments provided by the International Atomic Energy Agency (IAEA-412, IAEA-465, IAEA-385). 244Pu results are complemented with 239Pu, 240Pu, 241Pu and 236U and their relative isotopic abundances are discussed.

Fate of anthropogenic radionuclides (90Sr, 137Cs, 238Pu, 239Pu, 240Pu, 241Am) in seawater in the northern Benguela upwelling system off Namibia.

A baseline study on anthropogenic radioactivity in the Namibian marine ecosystem, which is part of the northern Benguela upwelling system, known as one of the most productive ocean areas in the world, has been performed. A scientific cruise carried out in 2014 covering inshore and offshore areas, exhibiting different oceanographic features, has provided a basis for better understanding the distributions, ratios and inventories of six anthropogenic radionuclides (90Sr, 137Cs, 238Pu, 239Pu, 240Pu and 241Am) in seawater. Although 3H was also measured, due to extremely low levels, its behaviour was not studied. The main source of 90Sr, 137Cs, 239Pu, 240Pu and 241Am in the samples analysed was proven to be global fallout, a finding further confirmed by 240Pu/239Pu and 90Sr/137Cs ratios. Furthermore, the 238Pu SNAP-9A satellite accident signal was confirmed once again through the determination of the 238Pu/239+240Pu activity ratio. Inshore and offshore samples showed different patterns due to the unique oceanographic features of this upwelling system. The levels of anthropogenic radionuclides, comprehensively assessed for the first time in this region, are comparable with the few existing data and filled a critical gap for the Southern Atlantic Ocean.

Insights into the Pu isotopic composition (239Pu, 240Pu, and 241Pu) and 236U in marshland samples from Madagascar.

This work provides new insights into the presence of 239Pu, 240Pu, 241Pu, and 236U in the Southern Hemisphere through the study of peat bog cores from marshlands in Madagascar (19°S). 210Pb, 238Pu and 239+240Pu activities were characterized by alpha spectrometry in previous studies. Here, Pu from alpha-spectrometry discs corresponding to 10 peat-bog cores (85 samples) was reassessed for the aim of completing its isotopic composition (239Pu, 240Pu, and 241Pu) by Accelerator Mass Spectrometry. In addition, 236U was studied in a single core exhibiting unusually low 240Pu/239Pu ratios. Integrated 240Pu/239Pu atom ratios in the single cores ranged above and below the (0-30°S) fallout average ratio, 0.173 ± 0.027, from 0.126 ± 0.003 to 0.206 ± 0.002, without a regional pattern, thereby demonstrating the heterogeneous distribution of the 239Pu and 240Pu signal. However, such a variability was not observed for 241Pu/239Pu, ranging from (6 ± 1) · 10-4 to (11 ± 1) · 10-4 and consistently below the (0-30°S) fallout ratio of (9.7 ± 0.3) · 10-4 (2012). The integrated 236U/239Pu atom ratio in the studied core, 0.147 ± 0.005, was also significantly lower than the values reported for the global fallout in the Northern Hemisphere, in the 0.20-0.23 range. Our results point out to stratospheric fallout as the main source of both 236U and 241Pu at the studied site, whereas 239Pu and 240Pu signals show the influence of tropospheric fallout from the low-yield tests conducted in Australia (1952-1958) by United Kingdom and in French Polynesia (1966-1975) by France despite the long relative distances (i.e. about 15,000 and 8500 km). It was also demonstrated that a representative number of samples is necessary in order to assess Pu contamination and its various origins in a specific region in the Southern Hemisphere due to the heterogeneous distribution, and results based on single sample analysis should be interpreted with caution.

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.

Comparative effects of seawater acidification on microalgae: Single and multispecies toxicity tests.

In order to gain knowledge about the potential effects of acidification in aquatic ecosystems, global change research based on microalgae as sentinel species has been often developed. However, these studies are limited to single species tests and there is still a research gap about the behaviour of microalgal communities under this environmental stressor. Thus, the aim of this study was to assess the negative effects of CO2 under an ecologically realistic scenario. To achieve this objective, two types of toxicity tests were developed; i) single toxicity tests and ii) multispecies toxicity tests, in order to evaluate the effects on each species as well as the interspecific competition. For this purpose, three microalgae species (Tetraselmis chuii, Phaeodactylum tricornutum and Nannochloropsis gaditana) were exposed to two selected pH levels (7.4, 6.0) and a control (pH 8.0). The pH values were choosen for testing different scenarios of CO2 enrichment including the exchange atmosphere-ocean (pH 7.4) and natural or anthropogenic sources of CO2 (pH 6.0). The effects on growth, cell viability, oxidative stress, plus inherent cell properties (size, complexity and autofluorescence) were studied using flow cytometry (FCM). Results showed that T. chuii was the most resistant species to CO2 enrichment with less abrupt changes in terms of cell density, inherent cell properties, oxidative stress and cell viability. Although P. tricornutum was the dominant species in both single and multispecies tests, this species showed the highest decrease in cell density under pH 6.0. Effects of competence were recorded in the multispecies control (pH 8) but this competence was eclipsed by the effects of low pH. The knowledge of biological interactions made by different microalgae species is a useful tool to extrapolate research data from laboratory to the field.

Presence of 236U and 239,240Pu in soils from Southern Hemisphere.

236U, 239Pu and 240Pu are present in soils mainly as a result of the local- and global-fallout from the atmospheric nuclear weapons tests carried out mainly in the 1950's and 1960's. In this work we provide new data on the presence of 236U and 239,240Pu in surface soils (i.e. up to 5 cm depth) from Chile and Africa. The results were obtained by low-energy Accelerator Mass Spectrometry (AMS). In the case of the Chilean samples, 236U/239Pu atom ratios show a high variability and are in general higher than the reported value for the global fallout in the Northern Hemisphere, ranging from 0.2 to 1.5. The 236U atomic concentrations range from 3.5 × 106 to 9.1 × 106 atoms/g, and are at least two orders of magnitude lower than the reported values in the Northern Hemisphere. The measured 240Pu/239Pu atom ratio in soils from South-Africa and Mozambique are of about 0.17, in agreement with the expected one for global-fallout at those coordinates. To best knowledge of the authors the present work is the first publication on 236U concentrations and 236U/239Pu atom ratios in soils from South-America and Africa.

Natural and artificial radionuclides in a marine core. First results of 236U in North Atlantic Ocean sediments.

There are very few data available of 236U in marine sediment cores. In this study we present the results from the first oceanic depth profile of 236U in a sediment core sampled in the North Atlantic Ocean, at the PAP site (4500 m depth, Porcupine Abyssal Plain (PAP) site, 49°0' N, 16°30' W). Additionally, the sediment core was radiologically characterized through the measurement of anthropogenic 137Cs, 239Pu, 240Pu, 129I and 14C and natural 210Pb, 40K and 226Ra. The measured 236U concentrations decrease from about 90·106 at g-1 at the seafloor down to 0.5·106 at g-1 at 6 cm depth. They are several orders of magnitude lower than the reported values for soils from the Northern Hemisphere solely influenced by global fallout (i.e. from 2700·106 to 7500·106 at g-1). 236U/238U atom ratios measured are at least three orders of magnitude above the estimated level for the naturally occurring dissolved uranium. The obtained inventories are 1·1012 at m-2 for 236U, 80 Bq m-2 for 137Cs, 45 Bq m-2 for 239+240Pu and 2.6·1012 at m-2 for 129I. Atomic ratios for 236U/239Pu, 137Cs/236U and 129I/236U, obtained from the inventories are 0.036, 0.11 and 2.5 respectively. Concentration profiles show mobilization probably due to bioturbation from the abundant detritivore holothurian species living at the PAP site sea-floor. The range of 236U, 137Cs, 239+240Pu and 129I values, inventories and ratios of these anthropogenic radionuclides are more similar to the values due to fall-out than values from a contribution from the Nuclear Fuel Reprocessing Plants dispersed to the south-west of the North Atlantic Ocean. However, signs of an additional source are detected and might be associated to the nuclear wastes dumped on the Eastern North Atlantic Ocean.

On the presence of plutonium in Madagascar following the SNAP-9A satellite failure.

This study examined the 238Pu and 239+240Pu activity concentration and the 240Pu/239Pu atomic ratio in peat bogs sampled in 2012 from marshlands in central Madagascar. The purpose was to investigate the presence of plutonium isotopes, 238, 239, 240Pu, from the 1964 satellite failure carrying a SNAP-9A radiothermal generator. With an average 238Pu/239+240Pu activity ratio of 0.165 ± 0.02 (decay corrected to 1964), the peat bogs in Madagascar exhibit similar values as the ones found in the southeastern African continent, except they are one order of magnitude higher than expected (0.025) from global fallout in the Southern Hemisphere. The 240Pu/239Pu atomic ratio showed a distinct decrease for layers dating back to the mid-1960s (down to 0.069 compared with an anticipated ratio of 0.17 for global fallout), indicating that the SNAP-9A failure also resulted in an elevated deposition of 239Pu. The obtained results demonstrate that further Pu analysis in Madagascar and in southeastern continental Africa is necessary to fully account for the regional Pu deposition from the SNAP-9A event.

Temporal evolution of 137Cs, 237Np, and 239+240Pu and estimated vertical 239+240Pu export in the northwestern Mediterranean Sea.

The evolution of 137Cs, 237Np and 239+240Pu at the DYFAMED station (NW Mediterranean) is discussed in relation to physical processes, downward fluxes of particles, and changes in the main input sources. The data set presented in this study represents the first complete 237Np vertical profiles (0.12-0.27µBqL-1), and constitutes a baseline measurement to assess future changes. A similar behavior of Cs and Np has been evidenced, confirming that Np behaves conservatively. While the 137Cs decrease has been driven by its radioactive decay, the vertical distribution of 237Np has not substantially changed over the last decade. In the absence of recent major inputs, a homogenization of their vertical distribution occurred, partly due to deep convection events that became more intense during the last decade. In contrast, 239+240Pu surface levels in the NW Mediterranean waters have fallen in the past four decades by a factor of 5. This decrease in surface has been balanced by higher concentrations in the deep-water layers. A first estimate of the downward 239+240Pu fluxes in the NW Mediterranean Sea is proposed over more than two decades. This estimation, based on the DYFAMED sediment trap time-series data and published 239+240Pu flux measurements, suggests that sinking particles have accounted for 60-90% of the upper layer (0-200m) Pu inventory loss over the period 1989-2013. The upper layer residence time of Pu is estimated to be ~28years, twice as long as the residence time estimated for the whole western Mediterranean (~15years). This difference highlights the slow removal of Pu in the open waters of the NW Mediterranean and confirms that most of the Pu removal occurs along the coastal margin where sedimentation rates are high.

A possible CO2 leakage event: Can the marine microbial community be recovered?

Bacterial communities have been studied to a much lesser degree than macrofauna in the case of a CO2 release. The resistance capacity of marine bacteria is well known, but their possible responses and their ability to recover after a CO2 release has not been investigated. Therefore, this work evaluated the responses of a marine bacterial community after 96h of CO2 exposure under diverse pH treatments (7.8 as control without CO2, 7.0, 6.5, and 6.0) and 24h after CO2 exposure. Results showed that the respiration activity and the diversity of the community were affected in all pH treatments. However, after 24h without CO2 enrichment, the respiration activity and diversity increased, showing a partial recovery. Consequently, bacterial responses have the potential to be used as a monitoring tool for risk assessment related to carbon capture and storage techniques or in any similar CO2 enrichment situations.

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.

Arctic Ocean sea ice drift origin derived from artificial radionuclides.

Since the 1950s, nuclear weapon testing and releases from the nuclear industry have introduced anthropogenic radionuclides into the sea, and in many instances their ultimate fate are the bottom sediments. The Arctic Ocean is one of the most polluted in this respect, because, in addition to global fallout, it is impacted by regional fallout from nuclear weapon testing, and indirectly by releases from nuclear reprocessing facilities and nuclear accidents. Sea-ice formed in the shallow continental shelves incorporate sediments with variable concentrations of anthropogenic radionuclides that are transported through the Arctic Ocean and are finally released in the melting areas. In this work, we present the results of anthropogenic radionuclide analyses of sea-ice sediments (SIS) collected on five cruises from different Arctic regions and combine them with a database including prior measurements of these radionuclides in SIS. The distribution of (137)Cs and (239,240)Pu activities and the (240)Pu/(239)Pu atom ratio in SIS showed geographical differences, in agreement with the two main sea ice drift patterns derived from the mean field of sea-ice motion, the Transpolar Drift and Beaufort Gyre, with the Fram Strait as the main ablation area. A direct comparison of data measured in SIS samples against those reported for the potential source regions permits identification of the regions from which sea ice incorporates sediments. The (240)Pu/(239)Pu atom ratio in SIS may be used to discern the origin of sea ice from the Kara-Laptev Sea and the Alaskan shelf. However, if the (240)Pu/(239)Pu atom ratio is similar to global fallout, it does not provide a unique diagnostic indicator of the source area, and in such cases, the source of SIS can be constrained with a combination of the (137)Cs and (239,240)Pu activities. Therefore, these anthropogenic radionuclides can be used in many instances to determine the geographical source area of sea-ice.

(239)Pu, (240)Pu, and (241)Am determination in hot particles by low level gamma-spectrometry.

A nondestructive method based on low-energy, high-resolution photon spectrometry is presented which allows accurate determination of (239)Pu, (240)Pu, and (241)Am (as a daughter of (241)Pu) activities in radioactive particles containing relatively high levels of plutonium isotopes. The proposed method requires only one measurement for the establishment of an absolute efficiency curve. Since the density and composition of the radioactive particles of interest may vary, a self-absorption correction is required for the accurate determination of isotopic activities and ratios. This correction is carried out for each individual particle using the convenient gamma-ray emissions of (241)Am.

Isolation of Pu-isotopes from environmental samples using ion chromatography for accelerator mass spectrometry and alpha spectrometry.

A radiochemical method for the isolation of plutonium-isotopes from environmental samples, based on the use of specific extraction chromatography resins for actinides (TEVA), Eichrom Industries, Inc.), has been set up in our laboratory and optimised for their posterior determination by alpha spectrometry (AS) or accelerator mass spectrometry (AMS). The proposed radiochemical method has replaced in our lab a well-established one based on the use of a relatively un-specific anion-exchange resin (AG) 1X8, Bio-rad Laboratories, Inc.), because it is clearly less time consuming, reduces the amounts and molarities of acid wastes produced, and reproducibly gives high radiochemical yields. In order to check the reliability of the proposed radiochemical method for the determination of plutonium-isotopes in different environmental matrixes, twin aliquots of a set of samples were prepared with TEVA and with AG 1X8 resins and measured by AS. Some samples prepared with TEVA resins were measured as well by AMS. As it is shown in the text, there is a comfortable agreement between AS and AMS, which adequately validates the method.

Brucellosis outbreak due to unpasteurized raw goat cheese in Andalucia (Spain), January - March 2002.

Eleven brucellosis cases were identified in three municipalities of Cordoba (Andalucia, Spain). A case-control study was conducted, selecting three cases per control. Persons having eaten unpasteurized raw goat cheese produced in a farmhouse located in the epidemic territory, were at higher risk for presenting brucellosis (OR=21.6, IC95%=1.6-639.8). Brucella melitensis serovar 3 was identified in clinical specimens and in goat tissue and milk samples from the herd's farmhouse. Preventive measures were implemented and the outbreak was stopped after the withdrawal of all suspicious cheeses from the market, additional sanitation of the farmhouse and health promotion activities.