Pu Deposition Research Articles

Anthropogenic plutonium radioisotopes in the ecosystem components of Sevastopol Bay (the Black Sea)

Modern levels (2010-2020) of 239+240Pu activity concentration in Sevastopol Bay (Black Sea) surface waters, 0-5 cm layer of bottom sediments and hydrobionts were determined by multistage radiochemical technique. The 239+240Pu activity concentrations in Sevastopol Bay surface water were on relatively low level: 1.08±0.09 - 1.54±0.17 mBqnr3. The maximum value of 239+240Pu activity concentration in the bottom sediments surface layer was observed in Sevastopol Bay mouth (993±90 mBqkg1) and it decreased with distance from the bay entrance to its tail end down to the minimum value - 276±53 mBqkg1. Based on these results as well as on published data the 239+240Pu deposition density distribution in the bay boxes and their inventory in 0-5 cm layer of bottom sediments were estimated in every boxes. Total 239+240Pu inventory in the bottom sediments surface layer was estimated at 121 MBq, with the highest deposition density value determined in the mouth part of the bay. Among studied hydrobiont species the highest 239+240Pu content was determined for mollusks (for their shells) Mytilus galloprovincialis (Lamarck, 1819) while the lowest - for fish Scorpaena poreus (Linnaeus, 1758). Accumulation ability of studied ecosystem components of Sevastopol Bay against 239+240Pu was characterized by evaluating concentration factors (Cf). It was shown that the bottom sediments of the bay were the main depot for plutonium anthropogenic radionucludes (Cf (239+240Pu) = n-105). The Cf (239+240Pu) were from two to three orders of magnitude lower for the hydrobionts of the bay: n-103 for brown algae and mollusks and n-102 for green algae and fish.

Soil erosion along a transect in a forested catchment: Recent or ancient processes?

Forested areas are assumed not to be influenced by erosion processes. However, forest soils of Northern Germany in a hummocky ground moraine landscape can sometimes exhibit a very shallow thickness on crest positions and buried soils on slope positions. The question consequently is: Are these on-going or ancient erosional and depositional processes? Plutonium isotopes act as soil erosion/deposition tracers for recent (last few decades) processes. Here, we quantified the 239+240Pu inventories in a small, forested catchment (ancient forest “Melzower Forst”, deciduous trees), which is characterised by a hummocky terrain including a kettle hole. Soil development depths (depth to C horizon) and 239+240Pu inventories along a catena of sixteen different profiles were determined and correlated to relief parameters. Moreover, we compared different modelling approaches to derive erosion rates from Pu data.We find a strong relationship between soil development depths, distance-to-sink and topography along the catena. Fully developed Retisols (thicknesses > 1 m) in the colluvium overlay old land surfaces as documented by fossil Ah horizons. However, we found no relationship of Pu-based erosion rates to any relief parameter. Instead, 239+240Pu inventories showed a very high local, spatial variability (36–70 Bq m−2). Low annual rainfall, spatially distributed interception and stem flow might explain the high variability of the 239+240Pu inventories, giving rise to a patchy input pattern. Different models resulted in quite similar erosion and deposition rates (max: −5 t ha−1 yr−1 to +7.3 t ha−1 yr−1). Although some rates are rather high, the magnitude of soil erosion and deposition - in terms of soil thickness change - is negligible during the last 55 years. The partially high values are an effect of the patchy Pu deposition on the forest floor. This forest has been protected for at least 240 years. Therefore rather natural events and anthropogenic activities during medieval times or even earlier must have caused the observed soil pattern, which documents strong erosion and deposition processes.

Characteristic of Pu from urban wetland and lacustrine sediments in Suzhou Industrial Park, China

In this study, plutonium activity concentrations in the urban wetlands and lacustrine sediment of Suzhou Industrial Park (SIP) are studied for the first time. Results show 239+240Pu activity concentrations in the wetland surface soils of SIP range from 0.035 to 0.426 mBq/g and the 240Pu/239Pu atom ratio ranges from 0.171±0.024 to 0.226±0.049. Judging from the atom ratio of 240Pu/239Pu, the main source of Pu in the wetland is global fallout. The correlations of Pu between organic matter and heavy metals are also studied. The correlation coefficients show Pu has significant positive correlations with Cu, Sn and Pb but negative correlation with As. Unlike distributions of Pu in other places, Pu in SIP has weak correlation with organic matter content. A sediment core from Lake Yangcheng is also analyzed to investigate the historical record of Pu deposition. The atom ratios of each layer in the sediment core indicate the area is mainly influenced by global fallout. Using Pu as a discrete-time maker, the deposition rate in Lake Yangcheng is 0.396±0.019 cm/yr. The calculated inventory of 239+240Pu is 58.5 Bq/m2, which is in the range of inventories of the corresponding latitudes according to UNSCEAR.

Fetuin exhibits a strong affinity for plutonium and may facilitate its accumulation in the skeleton

After entering the blood, plutonium accumulates mainly in the liver and the bones. The mechanisms leading to its accumulation in bone are, however, completely unknown. We already know that another uptake pathway not involving the transferrin-mediated pathways is suspected to intervene in the case of the liver. Fetuin, a protein playing an important role in bone metabolism, is proposed as a potential transporter of Pu from serum to bone. For the first time, the binding constants of these two proteins (transferrin and fetuin) with tetravalent plutonium at physiological pH (pH 7.0) were determined by using capillary electrophoresis (CE) coupled with inductively coupled plasma mass spectrometry (ICP-MS). Their very close values (log10 KPuTf = 26.44 ± 0.28 and log10 KPuFet = 26.20 ± 0.24, respectively) suggest that transferrin and fetuin could compete to chelate plutonium, either in the blood or directly at bone surfaces in the case of Pu deposits. We performed competition reaction studies demonstrating that the relative distribution of Pu-protein complexes is fully explained by thermodynamics. Furthermore, considering the average concentrations of transferrin and fetuin in the blood, our calculation is consistent with the bio-distribution of Pu observed in humans.

The speciation, transformation kinetics and fate of spiked Pu (IV) in highly saline groundwater

The mobility of plutonium (Pu) in groundwater is dependent of its speciation distribution and transformation. The speciation and transformation kinetics of Pu(IV) and its colloids in highly saline groundwater have, however, been rarely studied. In the present study, groundwater (Ionic strength 1 M) from Dunhuang region, NW China, was collected for investigating the speciation, transformation kinetics and fate of spiked Pu (IV) with aging time. The results showed that ~99% of the spiked Pu (IV) (over initial concentration c0 range 2.5 × 10−10–7.8 × 10−7 mol·L−1) was easily associated with the natural colloids and transformed into relatively unstable Pu pseudo-colloids in 1 day, which then gradually deposited and/or adsorbed on the container walls with aging. The suspended Pu pseudo-colloids decreased in similar exponential models, with rate equations r(t) = −3.1 × 10−10e– t/4 and −1.3 × 10−8e–/3 for c0 = 1.25 × 10−9 mol·L−1and 4.17 × 10−8 mol·L−1, respectively. The chemical speciation of the suspended colloidal Pu was dominated by “Fe/Mn Oxides” at the early time, while “Carbonates” with slower depositing rate (r(t) = −6.9 × 10−12e– 0.149t) dominated it (~82%) at equilibrium state. Whatever the c0 was, the concentration of dissolved Pu (i.e., the apparent solubility of Pu) kept at 0.7 × 10−11 mol·L−1 over aging. The valence of dissolved Pu was dominated by Pu(IV) at early time, while Pu(V + VI) would become dominant (~95%) at equilibrium state with transformation rate of r(t) = −92.9e– t/16.6 + 96.9. The equilibrium times of Pu deposition (and/or adsorption), speciation transformation of the suspended colloidal Pu, and valence change of the dissolved Pu were 30 d, 80 d and 120 d, respectively. The kinetic process for each Pu species could be well fitted with exponential model. These results suggest that the majority of released Pu(IV) into highly saline groundwater will be easily associated with natural aquatic colloids and then become immobile in short time due to deposition (and/or adsorption) onto the environmental medium, but potential migration risk caused by stable suspended Pu colloids cannot be ignored.

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.

Transient modeling of spent nuclear fuel electrorefining with liquid metal electrode

During the molten salt electrorefining of spent nuclear fuel, multiple phases such as oxide, solid metal, liquid metal, and molten salt often co-exist. Computational modeling can be a useful tool for understanding the reaction mechanism across the multiple phases. The new model has been developed and applied to a lab-scale electrorefining with liquid metal anode and solid cathode LiCl-KCl molten salt. The benchmark study predicts anodic dissolution and cathodic deposition of U and Pu with minor disagreements. In particular, the on-set of Pu deposition on the surface of the solid cathode is well estimated, which is important for the quality of U ingot and the safeguards of process. The underestimation of U deposition (∼6%) and the overestimation of Pu dissolution (∼7%) at the end of simulation are explained by unconsidered reaction species such as Np and Am from the liquid Cd anode, which overestimates the dissolution of Pu from the anode compared to the measured data. The sensitivity study also reveals the transition behaviors of electrochemical reactions for U and Pu on the solid cathode are changed by diffusion boundary layer thickness, transfer coefficients, and the difference of electrochemical potentials more sensitively than those of the liquid metal anode. For this specific experiment case, the thinner diffusion boundary layer improves the prediction of cathodic reactions particularly at the end of electrorefining.

Plutonium concentration and 240Pu/239Pu isotopic ratio in the surface soils from the Jiuquan region in northwestern China

Surface soil samples collected in the Jiuquan region in the downwind area of the Chinese nuclear test site (CNTs) were analyzed for Pu isotopes. The 239+240Pu activities ranged from 0.025 ± 0.009 to 0.89 ± 0.16 mBq g−1, varying significantly with different sampling sites. The Dunhuang city that is located in the southwestern part of the Jiuquan region received the heaviest Pu deposition (239+240Pu activities, 0.23–0.89 mBq g−1). Most of the 240Pu/239Pu isotopic ratios were similar with that of the global fallout. However, the low values (0.080–0.147) observed in three sampling sites further supported the finding of Pu originated from CNTs in that region.

Historical reconstruction of Plutonium contamination in the Swiss-Italian Alps

Plutonium is present in the environment as a consequence of atmospheric nuclear tests carried out in the 1960s, nuclear weapons production and releases by the nuclear industry over the past 50 years. Approximately 6 tons of 239 Pu have been released into the environment as a result of 541 atmospheric weapon tests Nuclear Pu fallout has been studied in various environmental archives, such as sediments, soil and herbarium grass. Mid-latitude ice cores have been studied as well, on Mont Blanc, the Western Alps and on Belukha Glacier, Siberian Altai. We present a Pu record obtained by analyzing 52 discrete samples of an alpine firn/ice core from Colle Gnifetti (M. Rosa, 4450 m a.s.l.), dating from 1945 to 1991. The 239 Pu signal was recorded directly, without preliminary cleaning or preconcentration steps, using an high resolution inductively plasma mass spectrometer equipped with a desolvation system. The 239 Pu profile reflects the three main periods of atmospheric nuclear weapons testing: the earliest peak lasted from 1954/55 to 1958 and was caused by the first testing period reaching a maximum in 1958. Despite a temporary halt of testing in 1959/60, the Pu concentration decreased only by half with respect to the 1958 peak due to long atmospheric residence times. In 1961/62 Pu concentrations rapidly increased reaching a maximum in 1963. After the signing of the Limited Test Ban Treaty between USA and USSR in 1964, Pu deposition decreased very sharply reaching a minimum in 1967. The third period (1967-1975) is characterized by irregular Pu concentrations with smaller peaks which might be related to the deposition of Saharan dust contaminated by the French nuclear tests of the 1960s.

Plutonium in Gorce Mountains area (Southern Poland)

Paper presents results of the plutonium deposition measurements in Gorce Mountains—a small part of western Polish Carpathians, Southern Poland where a national park was established in 1981. Samples were collected in both forest and alp areas. They were analyzed by means of alpha spectrometry preceded by radiochemical treatment. The results for activity concentration are then used to calculate cumulated deposition which range from 45.7 ± 4.3 to 164 ± 19 Bq/m2, what means that it reach in maximum almost three times higher value than UNSCEAR average for global fallout, expected for our latitude. The isotopic activity ratio 238Pu to 239+240Pu indicates global fallout as the main if not the only source of Pu. Nevertheless, presented results for plutonium reveal more uniform Pu deposition pattern in Gorce Mountains than it was observed for 137Cs in earlier study using the same samples.

Direct Determination of the Intracellular Oxidation State of Plutonium

Microprobe X-ray absorption near edge structure (μ-XANES) measurements were used to determine directly, for the first time, the oxidation state of intracellular plutonium in individual 0.1-μm(2) areas within single rat pheochromocytoma cells (PC12). The living cells were incubated in vitro for 3 h in the presence of Pu added to the media in different oxidation states (Pu(III), Pu(IV), and Pu(VI)) and in different chemical forms. Regardless of the initial oxidation state or chemical form of Pu presented to the cells, the XANES spectra of the intracellular Pu deposits were always consistent with tetravalent Pu even though the intracellular milieu is generally reducing.

Pu and137Cs in the Yangtze River Estuary Sediments: Distribution and Source Identification

Pu isotopes and (137)Cs were analyzed using sector field ICP-MS and γ spectrometry, respectively, in surface sediment and core sediment samples from the Yangtze River estuary. (239+240)Pu activity and (240)Pu/(239)Pu atom ratios (>0.18) shows a generally increasing trend from land to sea and from north to south in the estuary. This spatial distribution pattern indicates that the Pacific Proving Grounds (PPG) source Pu transported by ocean currents was intensively scavenged into the suspended sediment under favorable conditions, and mixed with riverine sediment as the water circulated in the estuary. This process is the main control for the distribution of Pu in the estuary. Moreover, Pu is also an important indicator for monitoring the changes of environmental radioactivity in the estuary as the river basin is currently the site of extensive human activities and the sea level is rising because of global climate changes. For core sediment samples the maximum peak of (239+240)Pu activity was observed at a depth of 172 cm. The sedimentation rate was estimated on the basis of the Pu maximum deposition peak in 1963-1964 to be 4.1 cm/a. The contributions of the PPG close-in fallout Pu (44%) and the riverine Pu (45%) in Yangtze River estuary sediments are equally important for the total Pu deposition in the estuary, which challenges the current hypothesis that the riverine Pu input was the major source of Pu budget in this area.

Contamination of Alpine snow and ice at Colle Gnifetti, Swiss/Italian Alps, from nuclear weapons tests

Plutonium is present in the environment as a consequence of atmospheric nuclear tests, nuclear weapons production and industrial releases over the past 50 years. To study temporal trends, a high resolution Pu record was obtained by analyzing 52 discrete samples of an alpine firn/ice core from Colle Gnifetti (Monte Rosa, 4450 m a.s.l.), dating from 1945 to 1990. The 239Pu signal was recorded directly, without decontamination or preconcentration steps, using an Inductively Coupled Plasma - Sector Field Mass Spectrometer (ICP-SFMS) equipped with an high efficiency sample introduction system, thus requiring much less sample preparation than previously reported methods. The 239Pu profile reflects the three main periods of atmospheric nuclear weapons testing: the earliest peak lasted from 1954/55 to 1958 and was caused by the first testing period reaching a maximum in 1958. Despite a temporary halt of testing in 1959/60, the Pu concentration decreased only by half with respect to the 1958 peak due to long atmospheric residence times. In 1961/62 Pu concentrations rapidly increased reaching a maximum in 1963, which was about 40% more intense than the 1958 peak. After the signing of the Limited Test Ban Treaty between USA and USSR in 1964, Pu deposition decreased very sharply reaching a minimum in 1967. The third period (1967-1975) is characterized by irregular Pu concentrations with smaller peaks (about 20-30% of the 1964 peak) which might be related to the deposition of Saharan dust contaminated by the French nuclear tests of the 1960s. The data presented are in very good agreement with Pu profiles previously obtained from the Col du Dome ice core (by multi-collector ICP-MS) and Belukha ice core (by Accelerator Mass Spectrometry, AMS). Although a semi-quantitative method was employed here, the results are quantitatively comparable to previously published results.

Depositional behaviors of plutonium and thorium isotopes at Tsukuba and Mt. Haruna in Japan indicate the sources of atmospheric dust

Monthly plutonium and thorium depositions at Tsukuba (28 m asl) and Mt. Haruna (1370 m asl) were measured during 2006 and 2007 (Jan 2006–Dec 2007 at Tsukuba, Nov 2006–Dec 2007 at Mt. Haruna). The monthly 239,240Pu depositions ranged from 0.044 to 2.67 mBq m −2 at Tsukuba and from 0.05 to 0.9 mBq m −2 at Mt. Haruna during the measurement periods. Monthly 239,240Pu deposition did not differ markedly between the two sites except in April 2007. Seasonal pattern of monthly 239,240Pu depositions at both sites showed high in spring and low in summer, and typical of seasonal variations in northeastern Asia. Thorium deposition at Tsukuba was higher than that at Mt. Haruna except in May and June 2007. 230Th/ 232Th activity ratios were used to partition deposition samples into locally and remotely derived fractions. The results revealed that a major proportion of total 239,240Pu and Th deposits are derived from remote sources, especially in spring.

Recent trends of plutonium fallout observed in Japan: Comparison with natural lithogenic radionuclides, thorium isotopes

Plutonium was determined in monthly atmospheric deposition samples from 2000 to the end of 2003 collected at Tsukuba, Japan, together with monthly thorium deposition. Monthly 239,240Pu and thorium depositions showed a typical seasonal variation with a maximum in spring. The 230Th/232Th activity ratios in the deposition samples differed from that of surface soils near Tsukuba. These results reveal that a significant part of the 239,240Pu deposition observed in Japan is attributable to resuspension of deposited plutonium originating from the East Asian continent deserts and arid areas.

Enhanced decorporation of plutonium by DTPA encapsulated in small PEG-coated liposomes

The aim of the study was to demonstrate that decorporation of 238Pu is achieved more efficiently by an optimized liposomal formulation of diethylene triamine pentaacetic acid (DTPA) than by the usual free DTPA treatment. The optimized formulation consisted of polyethylene glycol-coated stealth ® liposomes with a mean diameter of 100 nm (SL-100 nm). Rats were intravenously injected with various Pu-phytate salt solutions in order to test different contamination conditions (activity and salt concentration) impacting liver kinetics and skeletal uptake of Pu. All treatments were given intravenously 1 h after contamination. Efficiency was evaluated 24 h, 7, 16 or 30 days later through their ability to promote Pu elimination and to reduce Pu burden in the skeleton and liver, the main organs of Pu deposition and radiotoxicological effects. Whatever the conditions of contaminations, a single injection of SL-100 nm (3.2 μmol kg –1 DTPA) boosted urinary elimination of Pu to above 90% of the injected dose. In addition, liposomes strongly and significantly reduced the Pu burden of the liver and skeleton even 30 days after a single treatment: a dose of 0.3 μmol kg –1 induced the same skeletal Pu reduction as four injections of free DTPA (30 μmol kg –1). A log dose–effect relation was found with SL-100 nm DTPA and Pu excretion in urine or Pu burden in the studied organs (liver, femurs, spleen and kidneys). This efficacy was attributed to an optimized targeting of DTPA to the main Pu retention organs and especially the liver.

Wet and dry deposition patterns of plutonium in Daejeon, Korea

Plutonium in wet and dry deposition samples collected monthly at the Korea Institute of Nuclear Safety (KINS), Daejeon, Korea was determined during the period from January 2000 to August 2000. Monthly 239,240Pu deposition in Korea showed a maximum in the spring season (March to May), which was several times greater than that in Japan and corresponds to a seasonal cycle of soil dust fallout originating from the East Asian arid areas. The trajectory analysis of dust storms suggests that 239,240Pu deposition in Korea in spring is originating from plutonium-bearing surface soil particles from the East Asian arid areas. A significant part of the 239,240Pu deposition in spring in Korea is attributable to dry deposition.

Recent trends of plutonium fallout observed in Japan: plutonium as a proxy for desertification.

Plutonium in monthly deposition samples collected in Tsukuba (the Meteorological Research Institute), Japan from 1990 to end of 2001 is reported, together with monthly plutonium deposition in Nagasaki and Yonaguni in 2000. The annual deposition of (239,240)Pu during the period from 1990 to 2001 shows no systematic interannual variation. However, monthly (239,240)Pu depositions show a typical seasonal variation with a maximum in spring season (March to April), which corresponds to seasonal cycle of soil dusts originating from the East Asian arid area. Plutonium isotopic ratios in the deposition samples suggest that significant amounts of the recent (239,240)Pu deposition observed in Japan are attributed to the resuspension of plutonium-bearing surface soil particles; resuspended plutonium originates from the East Asian arid areas. The recent increased tendency of (239,240)Pu content in residues in deposition samples may reflect desertification in the East Asian continent.

Plutonium and other alpha emitters in mushrooms from Poland, Spain and Ukraine

The paper presents results on Pu, U and Th isotope activity concentration measurements in some mushroom samples collected in Poland, Spain and Ukraine. The sampling sites differ a lot with regard to observed levels of Pu, its origin and isotope ratios as well as the environmental properties. Some of the Polish samples were collected in the north-eastern part of the country with up to 30 Bq/m 2 of Chernobyl Pu deposition. Other Polish and the Spanish samples are from areas with almost exclusively global fallout Pu present. Ukrainian samples were collected in a highly contaminated area with a deposition of about 3.7 kBq/m 2 of Chernobyl 239+240Pu. The maximum 239+240Pu activity concentration was found equal to (54±4) Bq/kg (dw—dry weight) for a Ukrainian Cantharellus cibarius sample. Ukrainian samples have an extremely high radiocesium level, with maximum of (51±4) MBq/kg (dw). The maximum 239+240Pu activity concentration for Polish samples was (81±5) mBq/kg (dw) for Xerocomus badius. From the isotopic ratio in this sample it can be concluded that Chernobyl fallout is the origin of Pu. More than twice as large was the Spanish maximum for Hebeloma cylindrosporum but with only global fallout Pu. Some aspects of the transfer of nuclides to fruit bodies is discussed and in some cases the transfer factors or aggregation coefficients were calculated. Especially high transfer factors were found for Hebeloma cylindrosporum from Spain.

Lichen (sp. Cladonia) as a deposition indicator for transuranium elements investigated with the Chernobyl fallout

The feasibility of employing carpet-forming lichens (sp. Cladonia) as a measure for the deposition of transuranium elements was investigated with the Chernobyl fallout. In Finland, the deposition of these elements after the accident was very uneven. The highest deposition values for 238Pu, 239,240Pu, 241Am, 242Cm and 243,244Cm were 5.7, 3.0, 1.3, 98 and 0.025 Bq m −2, respectively. The amount of deposited 239,240Pu was, however, only some percent of the fallout of the nuclear test explosions of the 1950s and the 1960s. Instead, practically no 242Cm was released into the environment during the weapons' testing. The correlation between the refractory nuclides 238Pu, 239,240Pu, 241Am, 242Cm, 95Zr and 144Ce in lichen was high ( r = 0.709–0.979), but the correlation between the transuranium elements and volatile 137Cs was much lower ( r = 0.227–0.276). The calculated biological half-lives of Pu and Am in lichen were 730 and 320 days, respectively. The 238 Pu 239,240 Pu activity ratio in the top parts of lichen samples was 0.54 ± 0.02 corresponding to a burn-up value of 12 M Wd kg −1. The 238 Pu 239,240 Pu activity ratios of 0.43 and 0.69 measured from two isolated hot particles correspond to burn-up values of 10 and 14 MWdkg −1, respectively. The deposition values for plutonium obtained with lichen-carpet samples are comparable to the values obtained with surface peat samples collected in May 1986. The 239,240Pu deposition values are also in good agreement with values obtained from regional 95Zr deposition and 239,240 Pu 95 Zr activity ratio data ( r = 0.92).