Evaluation of uranium and plutonium isotopes in marine samples from Veracruz coastline (Mexico).

Activity ratios (A.R.) of 234U/238U and activity concentration of 238+234U and 239+240Pu were measured in collected seawaters and sand beach samples from various locations along of littoral of Mexican state of Veracruz. Uranium and plutonium were separated and concentrated in a liquid-liquid partition chromatography, afterwards, detected and analyzed by means of alpha spectrometric technique. The 234U/238U activity ratio (AR) ranges from 0.72 to 1.11 in sand beach and from 0.77 to 1.22 in seawater. The activity concentration was found in sea water from 0.31 to 1.94 Bq/L for 234+238U and from 15 to 137 µBq/L for 239+240Pu, in sand beach samples was found to be from 0.64 to 3.86 Bq/kg for 234+238U and from 33 to 249 µBq/kg for 239+240Pu.

240Pu/239Pu signatures allow refining the chronology of radionuclide fallout in South America.

Atmospheric nuclear tests (1945-1980) have led to radioactive fallout across the globe. French tests in Polynesia (1966-1974) may influence the signature of fallout in South America in addition to those conducted by USA and former USSR until 1963 in the Northern hemisphere. Here, we compiled the 240Pu/239Pu atom ratios reported for soils of South America and conducted additional measurements to examine their latitudinal distributions across this continent. Significantly lower ratio values were found in the 20-45° latitudinal band (0.04 to 0.13) compared to the rest of the continent (up to 0.20) and attributed to the contribution of the French atmospheric tests to the ultra-trace plutonium levels found in these soils. Based on sediment cores collected in lakes of Chile and Uruguay, we show the added value of measuring 240Pu/239Pu atom ratios to refine the age models of environmental archives in this region of the world.

Distribution and source of plutonium in sediments from the southern Gulf of Mexico.

Here, we report on new data (75 analyses) of plutonium (Pu) isotopes to elucidate activity concentrations, inventories, sources, and their transport from the ocean surface to the seafloor from a collection of six deep-sea sediment cores (depths ranging from 257 to 3739 m) in the southern Gulf of Mexico. Sediment cores collected from the continental shelf and upper slope region of the Gulf of Mexico showed 240Pu/239Pu ratios of 0.15 to 0.26, and 239+240Pu-inventories ranging from 14.7 to 33.0 Bq m-2. Inventories and ratios are consistent with global fallout Pu for this tropical region. In contrast, sediment cores collected from the lower slope region and abyssal plain showed low 240Pu/239Pu ratios of 0.07 to 0.13 and much lower 239+240Pu inventories below 6.8 Bq m-2. This implies that only a small fraction of the expected global fallout Pu has reached the deep-sea sediments. The low 240Pu/239Pu isotope ratios indicate that fallout from the Nevada testing site was an important source of Pu in deep-sea sediments, and that this Pu was likely more efficiently scavenged from the water column than Pu from global fallout. We estimated that up to 44% of the total inventory of 239+240Pu in deep-sea sediments is due to the Nevada source. Low values and a progressive decrease of 240Pu/239Pu ratios and 239+240Pu inventories with increasing water depth have been previously reported for the Gulf of Mexico. Analysis of Pu isotopes in two sediment traps from the upper slope regions shows 240Pu/239Pu ratios comparable to those observed in global fallout. These results indicate that global fallout Pu is currently the main source of Pu in sinking particles in the water column. Therefore, a significant fraction of global fallout Pu must still be present, either in a dissolved phase, or as biologically recycled material in the water column, or scavenged on the shelf and shelf break. Our results bring to light important questions on the application of Pu isotopes to establish sediment chronologies in deep-sea sediments, since global fallout features such as the 1963 maximum are not available.

Plutonium in coral archives: A good primary marker for an Anthropocene type section.

While we officially live in the Holocene epoch, global warming and many other impacts of global change have led to the proposal and wide adoption of the Anthropocene to define the present geological epoch. The Anthropocene Working Group (AWG) established that it should be treated as a formal stratigraphic unit, demonstrated by a reference level commonly known as "golden spike", still under discussion. Here we show that the onset of bomb-derived plutonium recorded in two banded massive corals from the Caribbean Sea is consistent (1955-1956 CE), so sites far from nuclear testing grounds are potentially suitable to host a type section of the Anthropocene. Coastal coral demonstration sites are feasible, could foster economic development, and may serve as focal points for scientific dissemination and environmental education.

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.

EXPERIMENTAL AND COMPUTATIONAL EVALUATION OF EFFECTIVE CENTRE FROM A LONG COUNTER AT NEUTRON METROLOGY LABORATORY IN BRAZIL.

A long counter detector was manufactured by the Institute of Advanced Studies (IEAV) and was characterised in the neutron low scattering room at Brazilian National Ionising Radiation Metrology Laboratory (LNMRI/IRD) to deploy a secondary Standard for neutron fluence. The effective centre was measured experimentally with 252Cf+D2O, 252Cf, 241AmBe and 238PuBe neutron sources, having average energies from 0.55 to 4.16 MeV. The experimental arrangement and detector construction were carefully reproduced in Monte Carlo simulations, and the computational results were found to be in good agreement with those from experiment.

IRRADIATOR SYSTEM FOR MANGANESE SULFATE BATH EFFICIENCY MEASUREMENTS USING A PLUTONIUM-BERYLLIUM NEUTRON SOURCE.

This study describes the use of a neutron irradiator system based on a plutonium-beryllium neutron source for MnSO4 solution activation for use to determine the MSB system efficiency. Computational simulations using Monte Carlo code were performed to establish the main characteristics of the irradiator system. Among the simulated geometries and volumes, semi-cylindrical shape with 84.5 cm3 of MnSO4 solution yielded the best option to be built. Activity measurements were performed with a high-pure germanium detector to validate the new irradiation system. Results showed an average efficiency and uncertainty of the experimental standard deviation of the mean: 5.742 × 10-4 ± 0.036 × 10-4 (coverage factor k = 1), for MSB system. Efficiency value obtained shows good correlation to other published methods (i.e. a relative difference of 0.07%). This alternative metrological method demonstrated the utility of neutron sources for the irradiation of solutions in metrology laboratories providing a cost-efficient alternative to nuclear reactors or particle accelerators.

Evaluation of Reference Urinary Excretion Concentrations of Selected Radionuclides Corresponding to Clinical Decision Guides for Application in Radiological and in Nuclear Emergencies.

Radiological or nuclear emergency situations could lead to incorporation of radionuclides by the population. Intakes of radionuclides can be evaluated through measurements of radionuclides present in organs and tissues, or in urinary and/or fecal excretion. In an emergency situation involving a large number of people, the decision to provide medical treatment to an individual will likely be based on a single measurement. For that purpose, the National Council on Radiation Protection and Measurements (NCRP) has presented the Clinical Decision Guide (CDG) quantity, which corresponds to an intake amount of a radionuclide by an individual for which treatment is recommended. However, the NCRP recommends using one-fifth of the CDG for pregnant women and children which could result in an effective or equivalent dose in excess of the dose constraint. Tables of reference urinary excretion concentrations which are associated with an intake of one CDG for inhalation and ingestion intake scenarios of several forms of 60Co, 90Sr, 137Cs, 192Ir, 238Pu, 239Pu and 241Am have been calculated and are presented for the following categories of members of the public: 3 months old, 1 y, 5 y, 10 y, 15 y, adult and pregnant woman.

Uranium and plutonium in anoxic marine sediments of the Santiago River mouth (Eastern Pacific, Mexico).

The uranium (U) and plutonium (Pu) content with depth in a sediment core collected in the continental shelf off the mouth of the Santiago River in the Mexican Pacific was studied to evaluate the contamination effects of the effluent of the Santiago-Lerma River as it moves into the sea. The large mass of terrestrial detritus delivered by the river influences the physicochemical and geochemical processes in the seafloor. Abnormal concentrations of U and Pu in sediments were examined as indicative of the effects of anoxic conditions. One of the indicators of pollution of seawater is the bacterial activity of the shallow seabed layer; and among the prevailing bacteria, the magnetotactic ones induce the formation of euhedral and framboidal shapes (pyrite). These pyrite entities are by-products of anoxic environments loaded with decomposing detrital material and are very abundant in the surface layers of the sediment core analyzed. The pyrite formation is the result of a biochemical reaction between iron and organic sulphur reduced by bacteria, and the pyrite entities precipitate to the seafloor. In the same upper zone of the profile, 238U is readily immobilized, while 234U is oxidized and dissolved in seawater by the effect of hot atom chemistry. This may cause the activity ratio (AR) 234U/238U disequilibrium (near 0.41). Furthermore, in the shallow layer of the sediment core, an abnormally high concentration of 239+240Pu was detected. In this upper layer, the activity concentrations found were 3.19 Bq kg-1 for 238U, 1.32 kg-1 for 234U and 2.78 Bq kg-1 for 239+240Pu. In the lower fractions of the sediment core, normal values of AR 234U/238U (≈1) were found, with traces of 239+240Pu.

The magnitude and relevance of the February 2014 radiation release from the Waste Isolation Pilot Plant repository in New Mexico, USA.

After almost fifteen years of successful waste disposal operations, the first unambiguous airborne radiation release from the Waste Isolation Pilot Plant (WIPP) was detected beyond the site boundary on February 14, 2014. It was the first accident of its kind in the 15-year operating history of the WIPP. The accident released moderate levels of radioactivity into the underground air. A small but measurable amount of radioactivity also escaped to the surface through the ventilation system and was detected above ground. The dominant radionuclides released were americium and plutonium, in a ratio consistent with the known content of a breached drum. The radiation release was caused by a runaway chemical reaction inside a transuranic (TRU) waste drum which experienced a seal and lid failure, spewing radioactive materials into the repository. According to source-term estimation, approximately 2 to 10Ci of radioactivity was released from the breached drum into the underground, and an undetermined fraction of that source term became airborne, setting off an alarm and triggering the closure of seals designed to force exhausting air through a system of filters including high-efficiency-particulate-air (HEPA) filters. Air monitoring across the WIPP site intensified following the first reports of radiation detection underground to determine the extent of impact to WIPP personnel, the public, and the environment, if any. This article attempts to compile and interpret analytical data collected by an independent monitoring program conducted by the Carlsbad Environmental Monitoring & Research Center (CEMRC) and by a compliance-monitoring program conducted by the WIPP's management and operating contractor, the Nuclear Waste Partnership (NWP), LLC., in response to the accident. Both the independent and the WIPP monitoring efforts concluded that the levels detected were very low and localized, and no radiation-related health effects among local workers or the public would be expected.

Source term estimation and the isotopic ratio of radioactive material released from the WIPP repository in New Mexico, USA.

After almost 15 years of operations, the Waste Isolation Pilot Plant (WIPP) had one of its waste drums breach underground as a result of a runaway chemical reaction in the waste it contained. This incident occurred on February 14, 2014. Moderate levels of radioactivity were released into the underground air. A small portion of the contaminated underground air also escaped to the surface through the ventilation system and was detected approximately 1 km away from the facility. According to the source term estimation, the actual amount of radioactivity released from the WIPP site was less than 1.5 mCi. The highest activity detected on the surface was 115.2 µBq/m(3) for (241)Am and 10.2 µBq/m(3) for (239+240)Pu at a sampling station located 91 m away from the underground air exhaust point and 81.4 µBq/m(3) of (241)Am and 5.8 µBq/m(3) of (239+240)Pu at a monitoring station located approximately 1 km northwest of the WIPP facility. The dominant radionuclides released were americium and plutonium, in a ratio that matches the content of the breached drum. Air monitoring across the WIPP site intensified following the first reports of radiation detection underground to determine the extent of impact to WIPP personnel, the public, and the environment. In this paper, the early stage monitoring data collected by an independent monitoring program conducted by the Carlsbad Environmental Monitoring & Research Center (CEMRC) and an oversight monitoring program conducted by the WIPP's management and operating contractor, the Nuclear Waste Partnership (NWP) LLC were utilized to estimate the actual amount of radioactivity released from the WIPP underground. The Am and Pu isotope ratios were measured and used to support the hypothesis that the release came from one drum identified as having breached that represents a specific waste stream with this radionuclide ratio in its inventory. This failed drum underwent a heat and gas producing reaction that overpowered its vent and lifted its lid to allow release of waste into the underground air.

236U/238U and 240Pu/239Pu isotopic ratios in small (2 L) sea and river water samples.

Accelerator Mass Spectrometry (AMS) and alpha spectrometry were used to determine uranium ((236)U, (238)U, (234)U) and plutonium isotopes ((239)Pu, (240)Pu) in sea and river water samples. Plutonium was separated by Dowex(®) 1 × 8 resin and UTEVA(®) resin was used for uranium purification. The measured (236)U/(238)U isotopic ratios for surface water from the Atlantic Ocean, the Pacific Ocean and the Black Sea were in the order of 10(-9), while values for river water were in the order of 10(-8). These contaminations may be attributed to global fallout. A sample of the reference material IAEA-443, collected from the Irish Sea, showed, in accordance to the reference value, a ratio that was 10(3) times higher due to effluents from the reprocessing plant at Sellafield. These results underline the good suitability of (236)U/(238)U as a tracer for hydrology and oceanography, and show that relatively small water samples are sufficient for the determination of (236)U by AMS, which is not the case for plutonium with present techniques. The plutonium concentrations in our water samples could only be measured with large uncertainties and were in the order of 10(-3) mBq/L (with the exception of the Irish Sea sample).

Vertical distribution and inventories of (239+240)Pu and mercury in Sagua la Grande estuary, Cuba.

The vertical activity distribution and inventories of (239+240)Pu profile and Hg were determined in Sagua la Grande estuary, Cuba. The shape of the (239+240)Pu profile in the core column resembled very closely the history of atmospheric nuclear weapons' testing, and the maximum deposition in 1963 was recorded in the sediment core history. The (239+240)Pu activity concentrations in the surface layer sediments varied from 0.163 to 0.611 mBq g(-1). The inventory of (239+240)Pu was 42 ± 5.6 Bq m(-2), a value close to that expected from direct global fallout. Using the (239+240)Pu as a chronomarker the mass sedimentation rate in the area for the last 60 years was calculated, reaching values of 0.173 g cm(-2) y(-1). The mercury profile reflects the history of anthropogenic pollution in the estuary and perfectly describes the operation of the mercury-cell chlor-alkali plant, for production of NaOH, which began operations in 1980. The inventory of Hg was 2.42 ± 0.19 µg cm(-2). These results contribute to the scarce regional database for pollutants and anthropogenic radionuclides in the Caribbean marine environment, particularly in relation to (239+240)Pu.

Dose-dependent analysis of acute medical effects of mixed neutron-gamma radiation from selected severe 235U or 239Pu criticality accidents in USSR, United States, and Argentina.

Eight of the most severe cases of acute radiation disease (ARS) known to have occurred in humans (as the result of criticality accidents) had survival times less than 120 h (herein defined as "early death"). These accidents were analyzed and are discussed with respect to the specific accident scenarios and the resulting accident-specific, mixed neutron-gamma radiation clinical dose distributions. This analysis concludes that the cardiovascular system appears to be the most critical organ system failure for causing "early death" following approximate total body, mixed gamma-neutron radiation doses greater than 40-50 Gy. The clinical data also suggest that there was definite chest dose dependence in the resulting survival times for these eight workers, who unfortunately suffered profound radiation injury and unusual clinical effects from such high dose radiation exposures. In addition, "toxemic syndrome" is correlated with the irradiation of large volumes of soft tissues. Doses to the hands or legs greater than 80-100 Gy or radiation lung injury also play significant but secondary roles in causing "early death" in accidents delivering chest doses greater than 50 Gy.

Uranium-series constraints on radionuclide transport and groundwater flow at the Nopal I uranium deposit, Sierra Pena Blanca, Mexico.

Uranium-series data for groundwater samples from the Nopal I uranium ore deposit were obtained to place constraints on radionuclide transport and hydrologic processes for a nuclear waste repository located in fractured, unsaturated volcanic tuff. Decreasing uranium concentrations for wells drilled in 2003 are consistent with a simple physical mixing model that indicates that groundwater velocities are low ( approximately 10 m/y). Uranium isotopic constraints, well productivities, and radon systematics also suggest limited groundwater mixing and slow flow in the saturated zone. Uranium isotopic systematics for seepage water collected in the mine adit show a spatial dependence which is consistent with longer water-rock interaction times and higher uranium dissolution inputs at the front adit where the deposit is located. Uranium-series disequilibria measurements for mostly unsaturated zone samples indicate that (230)Th/(238)U activity ratios range from 0.005 to 0.48 and (226)Ra/(238)U activity ratios range from 0.006 to 113. (239)Pu/(238)U mass ratios for the saturated zone are <2 x 10(-14), and Pu mobility in the saturated zone is >1000 times lower than the U mobility. Saturated zone mobility decreases in the order (238)U approximately (226)Ra > (230)Th approximately (239)Pu. Radium and thorium appear to have higher mobility in the unsaturated zone based on U-series data from fractures and seepage water near the deposit.

Determination of total content and isotopic compositions of plutonium and uranium in environmental samples for safeguards purposes by ICP-QMS.

The aim of this work was to determine the concentrations and isotopic compositions of plutonium and uranium in environmental samples for safeguards purposes. An analytical method was developed with a plutonium and uranium separation procedure based on extraction chromatography (using 2mL TEVA and UTEVA columns) and detection with a quadrupole ICP-MS applying an ultra-sonic nebulizer coupled with a membrane desolvation system. Starting from blank swipes, the background equivalent concentration (BEC) was 8fg for (239)Pu and 1ng (238)U. The method was successfully applied to certified reference materials as well as to round robin samples obtained in the framework of the inter-laboratory exercise program, promoted by the Brazilian-Argentine Agency for Accounting and Control of Nuclear Materials (ABACC), together with the US Department of Energy (USDOE). After the introduction of an additional ion-exchange separation step, the methodology was applied to the IAEA-384 sediment reference sample with precise and accurate total plutonium and uranium, (240)Pu/(239)Pu, (241)Pu/(239)Pu, (234)U/(238)U and (235)U/(238)U atomic ratio results.

Ultra-low level plutonium isotopes in the NIST SRM 4355A (Peruvian Soil-1).

For more than 20 years, countries and their agencies which monitor radionuclide discharge sites and storage facilities have relied on the National Institute of Standards and Technology (NIST) Standard Reference Material (SRM) 4355 Peruvian Soil. Its low fallout contamination makes it an ideal soil blank for measurements associated with terrestrial-pathway-to-man studies. Presently, SRM 4355 is out of stock, and a new batch of the Peruvian soil is currently under development as future NIST SRM 4355A. Both environmental radioanalytical laboratories and mass spectrometry communities will benefit from the use of this SRM. The former must assess their laboratory procedural contamination and measurement detection limits by measurement of blank sample material. The Peruvian Soil is so low in anthropogenic radionuclide content that it is a suitable virtual blank. On the other hand, mass spectrometric laboratories have high sensitivity instruments that are capable of quantitative isotopic measurements at low plutonium levels in the SRM 4355 (first Peruvian Soil SRM) that provided the mass spectrometric community with the calibration, quality control, and testing material needed for methods development and legal defensibility. The quantification of the ultra-low plutonium content in the SRM 4355A was a considerable challenge for the mass spectrometric laboratories. Careful blank control and correction, isobaric interferences, instrument stability, peak assessment, and detection assessment were necessary. Furthermore, a systematic statistical evaluation of the measurement results and considerable discussions with the mass spectroscopy metrologists were needed to derive the certified values and uncertainties. The one sided upper limit of the 95% tolerance with 95% confidence for the massic (239)Pu content in SRM 4355A is estimated to be 54,000 atoms/g.

Application of ICP-QMS for the determination of plutonium in environmental samples for safeguards purposes.

Aiming to determine the plutonium amount as well as its isotopic composition, in particular, in swipe samples for safeguards purposes, an analytical method was developed with a plutonium separation step based on extraction chromatography using 2 cm TEVA columns and detection with quadrupole ICP-MS applying an ultra-sonic nebulizer coupled with membrane desolvation system. The method was successfully applied to New Brunswick plutonium certified reference materials as well as to Lawrence Livermore National Laboratory round robin samples, based on the round robin samples provided by the Institute for Reference Materials and Measurements (Belgium), as part of the Regular European Interlaboratory Measurement Evaluation Programme (REIMEP), campaign 16 (isotopic abundances of plutonium in plutonium nitrate samples), with a total plutonium amount between 1 and 0.25 ng per sample. After the introduction of an additional separation step, it was also possible to carry out precise and accurate total plutonium, (240)Pu/(239)Pu, (241)Pu/(239)Pu and (242)Pu/(239)Pu atom ratios determination in sediment sample showing its applicability to environmental samples in general, reaching a detection limit equivalent to 5 mBq(239)Pu kg(-1).

Distribution of 137Cs, 238Pu and 239+240 Pu in sediments of the southeastern Brazilian shelf-SW Atlantic margin.

In this work levels of 137Cs, 238Pu and 239+240 Pu as well as activity ratios of anthrophogenic radionuclides in sediment samples from the southeastern Brazilian shelf are presented. Instrumental gamma spectrometry was used to determine 137Cs and alpha spectrometry to determine 238Pu and 239+240 Pu after a radiochemical procedure. The levels ranged from 0.30 to 1.79 Bq kg(-1) for 137Cs, from 15 to 150 mBq kg(-1) for 238Pu and, from 18 to 117 mBq kg(-1) for 239+240 Pu. There was a bathymetric differentiation in the radionuclides distribution. 137Cs values were generally higher in the samples collected at water depths of less than 100 m. On the other hand, plutonium isotopes exhibit higher values at greater depths. The mean ratio of 239+240 Pu/137Cs obtained was 0.112+/-0.072 which is in agreement with the value reported for the Atlantic from atmospheric fallout of nuclear explosions in the past. The 238Pu/230+240 Pu ratios varied widely (from 0.339 to 2.088) and showed the influence of the SNAP-9A accident in the 238Pu levels for this area. The main goal of this work was to present unpublished anthropogenic radionuclide levels and activity ratios related to the contamination of the southeastern Brazilian shelf.