Behaviour of239,240Pu and241Am in the Baltic Sea; Measurements and interpretation in 1980–1984

Concentrations of^239,240Pu and²⁴¹Am in filtered seawater, particulate fraction and sediment were measured. Methods for determination of these nuclides were critically chequed and a new rapid method for²⁴¹Am in sediment was developed. Due to seasonal variation a significant decrease of plutonium and americium concentrations in surface water takes place in summer. Americium is more efficiently associated with particulate matter than plutonium. From May 1980 to September 1984 soluble plutonium in the water was reduced to about half. The residence half-time of^239,240Pu in the water of Baltic Sea is of the order of 5 years. About similar concentrations of^239,240Pu and²⁴¹Am were found in particulates in water as in the surface layer of the sediment. The average K_d-values for plutonium and americium were 10⁵ and 10⁵–10⁶ ml/g, respectively.     

241Pu concentration in southern Baltic Sea ecosystem

Summary ²⁴¹Pu concentrations were calculated indirectly in different compartments of the southern Baltic ecosystem by the activity measurements of²⁴¹Am isotope from the increase of the<span lang=EN-GB style='font-size:12.0pt;font-family:Symbol;mso-bidi-font-family:Symbol; mso-ansi-language:EN-GB'>b-emitting²⁴¹Pu at 16-18 years after the Chernobyl accident. Enhanced levels of²⁴¹Pu were observed in all analyzed samples. Maximum values (0.408 and 0.367 mBq^. g^-1d.w.) of the estimated²⁴¹Pu concentrations were found in sediments of Internal Puck Bay and Gdańsk Bay, respectively, and in the suspended matter from water of Gdańsk Bay (77.8 mBq^.g^-1d.w.). The highest²⁴¹Pu/^239+240Pu activity ratio was found in the suspended matter (1500) and water (140). The²⁴¹Pu activity of the air dust was very high in April 1986, 3643±34.3 mBq^.g^-1d.w., and the²⁴¹Pu/^239+240Pu activity ratio was 56, but the highest²⁴¹Pu/^239+240Pu activity ratio of the air dust was measured in August. Then the²⁴¹Pu concentration in air dust decreased quickly to values similar to those before the Chernobyl accident.<span style='font-size:12.0pt'>This study provides new data for the ²⁴¹Pu concentrations in various compartments of the Baltic Sea ecosystem.     

240Pu/239Pu atom ratios in the bottom sediments of the NW Pacific Ocean

^239+240Pu concentrations and ²⁴⁰Pu/²³⁹Pu atom ratios in bottom sediments of the Yellow Sea, Korea Strait, East Sea (Sea of Japan), Sea of Okhotsk, and Northwest Pacific Ocean were determined. In coastal sediments near the Korean Peninsula, ^239+240Pu concentrations varied from 0.02 to 1.72 Bq^.kg^-1, and their ²⁴⁰Pu/²³⁹Pu atom ratios from 0.15 to 0.24, with an average of 0.20±0.03. ²⁴⁰Pu/²³⁹Pu atom ratios of bottom sediments in the deep NW Pacific Ocean and its marginal seas (East, Okhotsk seas) were in the range of 0.15-0.23. A little elevated ²⁴⁰Pu/²³⁹Pu atom ratios in the bottom layer sediment may be due to Pu released into the environment during the pre-moratorium period, having high ²⁴⁰Pu/²³⁹Pu atom ratios and low ²³⁸Pu/^239+240Pu activity ratios.     

Sources of carbon isotopes in Baltic Sea sediments

Journal of Radioanalytical and Nuclear Chemistry - Radiocarbon and specific phospholipid-derived biomarkers were used to trace chemical warfare agents (CWA) at the Gotland Deep dumping site of...     

Effect of natural clay components on sorption of Cs, Pu and Am by the clay

Sorption of Cs, Pu and Am on natural clay of complex composition was studied to better understand the sorption mechanisms. It was found that cesium sorption to natural clay was affected by its coatings and by the ionic strength of solution. The sorption of Pu and Am on the clay was compared with that on synthetic goethite, hematite and magnetite, representing components of the clay coatings. The sorption was quantitatively interpreted using models assuming ion exchange and/or complex formation on the “layer sites” and “edge sites” of the clay and its coatings. Constants characterizing properties of the sites and sorption equilibria were determined.     

239Pu, 240Pu, 241Pu, 241Am, 137Cs,and 210Pb in seafloor sediments in the western North Pacific Ocean and the Sea of Japan: distributions,sources and budgets

Journal of Radioanalytical and Nuclear Chemistry - Vertical distributions of 239Pu, 240Pu, 241Pu, 241Am, 137Cs, and 210Pb concentrations, and 240Pu/239Pu ratios were determined in seafloor...     

Distribution and behaviour of99Tc,237Np,239,240Pu,and241Am in the coastal and estuarine sediments of the Irish Sea

Intertidal coastal and estuarine sediments from 24 sites in the Irish Sea have been analyzed for⁹⁹Tc,²³⁷Np,²³⁸Pu,^239,240Pu and²⁴¹Am. The²³⁷Np activity and²³⁹Pu/²⁴⁰Pu ratio were measured simultaneously by ICP-MS, and⁹⁹Tc was determined by HR-ICP-MS which is ten times more sensitive than Q-ICP-MS.The activities of⁹⁹Tc,²³⁷Np,^239,240Pu and²⁴¹Am were distributed over a wide range of 1.5–70.5, 0.01–13.3, 2.3–1589, 2.6–1894 Bq/kg, respectively. Activities of these radionuclides decreased exponentially with distance from the Sellafield source. The²⁴¹Am/^239,240Pu and²³⁷Np/^239,240Pu ratios were almost constant with distance from the Sellafield. This result suggests that the distribution and behavior of Np and Pu are controlled by complicated factors such as the influence of transport, the variation with time of Np/Pu ratio in the Sellafield discharges and sedimentary mixing processes in the Irish Sea.     

Presence of 137Cs, Pu isotopes and 241Am in ligurian and Tyrrhenian Seas sediments

During the last ten years, the Italian Universities of Parma and Urbino collaborated on a special radioecological program having the aim to study the levels and the distribution of long-lived radionuclides in different marine and terrestrial matrixes. This paper summarizes the results concerning the concentrations of ^239+240Pu and ²³⁸Pu, ²⁴¹Am and ¹³⁷Cs in sediments collected in the Ligurian and South Tyrrhenian Seas (Rapallo Harbour, Vado Ligure Canyon, Eolie Islands). Superficial sediments and sediment cores were collected. For cores the vertical distribution was calculated and the sedimentation rate obtained. ¹³⁷Cs was determined directly by gamma-spectrometry, while ^239+240Pu, ²³⁸Pu and ²⁴¹Am were separated by extraction chromatography, electroplating and determined by alpha-spectrometry. This revised version was published online in August 2006 with corrections to the Cover Date.     

Radioanalytical approach to determine 238Pu, 239+240Pu, 241Pu and 241Am in soils

The simultaneous determination of multiple actinide isotopes in samples where total quantity is limited can sometimes present a unique challenge for radioanalytical chemists. In this study, re-determination of ²³⁸Pu, ^239+240Pu, and ²⁴¹Am for soils collected and analyzed approximately three decades ago was the goal, along with direct determination of ²⁴¹Pu. The soils had been collected in the early 1970’s from a shallow land burial site for radioactive wastes called the Subsurface Disposal Area (SDA) at the Idaho National Lab (INL), analyzed for ²³⁸Pu, ^239+240Pu, and ²⁴¹Am, and any remaining soils after analysis had been archived and stored. We designed an approach to reanalyze the ²³⁸Pu, ^239+240Pu, and ²⁴¹Am and determine for the first time ²⁴¹Pu using a combination of traditional and new radioanalytical methodologies. The methods used are described, along with estimates of the limits of detection for gamma-and alpha-spectrometry, and liquid scintillation counting. Comparison of our results to the earlier work documents the ingrowth of ²⁴¹Am from ²⁴¹Pu, and demonstrates that the total amount of ²⁴¹Am activity in these soil samples is greater than would be expected due to ingrowth from ²⁴¹Pu decay.     

Fractionation and speciation analysis of heavy metals in the Azov Sea bottom sediments

The fractionation and speciation analysis of heavy metals in bottom sediment samples from the Azov Sea were performed. Seven-step sequential extraction was used to extract element species differing in physicochemical mobility and biological availability. Special attention was paid to the study of ecologically valuable mobile fractions: exchangeable, acid-soluble, readily reducible, and readily oxidizable ones. It was shown that the total concentration of mobile copper, zinc, and lead species isolated in four extraction steps was higher than the MPCs for mobile species extractable with an ammonium acetate buffer solution (1.1–3.3 PMC), which points to the technogenic contamination of bottom sediments and their potential hazard to hydrobionts. For finely dispersed silt samples taken near the Kerch Strait, elevated concentrations of zinc and copper (up to 10 and 5 mg/kg, respectively) were found in the most mobile exchangeable fraction directly available to living organisms, which indicates the presence of an active contamination source in this water area. The binding of metals to mineral phases in samples of different lithological types was studied.     

Experimental study and modelling of 137Cs sorption behaviour in the Baltic Sea and the Curonian Lagoon

Sorption–desorption behaviour of ¹³⁷Cs in the Baltic Sea and the Curonian Lagoon was studied in 1997–2009 with the aim to better understand processes responsible for redistribution and sink of ¹³⁷Cs in the system. Data obtained from several sampling campaigns were analyzed and short and long-term kinetic tracer experiments using natural water and bottom sediments were carried out with particles of various sizes from 0.2 to 50 μm. Samples of suspended particles and bottom sediments collected during two sampling campaigns were fractionated according to the size, and association of ¹³⁷Cs with solid phase was studied using sequential extraction. The difference in ¹³⁷Cs behaviour observed between expeditions in 1999 and 2001 was attributed to seasonal variations in chemical composition of suspended particles entering the system and consequent differences between the sorption (in 1999) and the desorption (in 2001) of ¹³⁷Cs in sea water. Data obtained from tracer kinetic sorption experiments with ¹³⁴Cs and bottom sediment fractions of different grain size were used for finding a suitable kinetic sorption model, kinetic constants and the corresponding equilibrium K _d values. It has been found that the modelled data best conform to the mechanism of ion diffusion through the so-called inert layer on the surface of the sediment particles.     

Distribution of global fallout237Np,Pu isotopes,and241Am in lake and sea sediments

In order to investigate the sedimentary behaviour of neptunium,²³⁷Np together with Pu isotopes and²⁴¹Am have been measured for the sediment cores collected from Lake Mikata (freshwater) and from Lake Kugushi (brakish water) both belonging to the Mikata Five Lakes, and from Nyu Bay (sea water). In all sediment core samples²³⁷Np was detected, and its concentrations were far below those of^239,240Pu and²⁴¹Am measured for the same samples. Inventories of²³⁷Np in Lake Mikata, Lake Kugushi and Nyu Bay were estimated to be 0.53, 0.29 and 0.34 MBq/km², respectively. The activity ratio of²³⁷Np/^239,240Pu calculted from the inventories in each sediment core was 0.29% for Lake Mikata, 0.15% for Lake Kugushi and 0.10% for Nyu Bay. These values except for the value for Lake Mikata are two or three times lower than the value of 0.3–0.4% observed for surface soils of 0–20 cm depth, suggesting that Np is more soluble compared with Pu.     

Theoretical study of Pu and Am tetracarbide molecules

The electronic structure and ground‐state molecular properties of Pu and Am tetracarbides have been investigated by relativistic multireference calculations using CASSCF/CASPT2 theory as well as by density functional theory in conjunction with relativistic pseudopotentials. The CASSCF/CASPT2 treatment has been extended by spin–orbit coupling effects for selected species using the CAS state‐interaction method. The five atoms can form various structural isomers, from which 12 ones have been identified in our study. The electronic ground state in both molecules corresponds to a planar fan‐type structure of C_2v symmetry, in which the actinide atom is connected to a bent C₄ moiety. The other structures are much higher in energy, the ones computed in this study appear between 250 and 1050 kJ/mol. The bonding characteristics in the most relevant structures have been analyzed on the basis of the valence molecular orbitals and natural bond orbital analysis. The most stable structures have been characterized by their spectroscopic (vibrational and electron) properties. © 2014 Wiley Periodicals, Inc.     

Study of Am and Pu behavior in alkaline media

The redox chemical behavior of americium and plutonium species in alkaline media has been studied, mainly two dis/reproportionation reactions: 2 Pu(VI) = Pu(V) + Pu(VII) and Am(III) + Am(V) = 2Am(IV). It was found that Am(VI) is readily reduced by the simple action of water, and that radiolysis has no effect. This is a marked departure from the behavior of Am in other media, where alpha particle self-irradiation generates redox active species that affect the Am oxidation state. An Am(VII) compound has been synthesized. All results are interesting for the treatment of alkaline high-level radioactive wastes. To cite this article: A.P. Nikonov et al., C. R. Chimie 7 (2004).

Résumé

Étude du comportement de Am et Pu en milieu alcalin. Le comportement redox de Am et Pu a été étudié en milieu alcalin, notamment les dismutations 2 Pu(VI) = Pu(V) + Pu(VII) et 2 Am(IV) = Am(III) + Am(V). Am(VI) est rapidement réduit par l’eau et la radiolyse n’a pas d’effet, contrairement à ce qui se produit dans d’autres milieux. Des indications ont été obtenues sur un composé de Am(VII). Les résultats obtenus sont intéressants pour le traitement des déchets nucléaires encore entreposés en milieu basique. Pour citer cet article : A.P. Nikonov et al., C. R. Chimie 7 (2004).     

Quantification of thorium and uranium sorption to contaminated sediments

Desorption tests, using a sequential extraction method, were used to characterize and quantify thorium and uranium sorption to contaminated wetland sediments collected from the Department of Energy's Savannah River Site located in South Carolina. In situ distribution coefficients, or K _d values (K _d = C _solid/C _liquid), were determined. Sequential extraction data were used to assign solid-phase radionuclide concentrations (C _solid) that, by definition, should represent only the reversibly sorbed fraction. A series of selective and sequential extractions was used to determine desorption K _d values. Thorium K _d values ranged from 115 to 2255 ml/g. Uranium K _d values ranged from 170 to 6493 ml/g. Compared to sorption K _d values, these desorption K _d values were appreciably greater because they captured the aging process of the radionuclides with the sediment, making the radionuclide more refractory. Compared to nonsite-specific data, these in situ K _d values improved accuracy, were more defensible, and removed unnecessary conservatism for subsequent transport and risk calculations. Additional tests were conducted to provide geochemical information relevant for selecting appropriate remediation technologies for the contaminated site. Thorium and uranium were associated with labile fractions and were not concentrated with the smaller sediment particles. These findings suggest that phytoremediation or heap leaching, and not soil washing, are viable remediation approaches for this site.     

Sediment sample preparation for the determination of Pu and Am isotopes

Summary Sediment samples from the Romanian sector of the Danube River and the Black Sea coast were analyzed for Pu and Am. Three different ways of bringing the samples into solution were tested: acid attack, microwave digestion and alkaline fusion. A conventional anion-exchange resin was used to separate plutonium from other radionuclides and several variants were tried to improve the separation of americium. The preparation of thin sources for alpha-spectrometry was tested through electrodeposition and coprecipitation with Nd(III). Discussion and recommendations for the dissolution step, the americium separation and preparation of alpha sources are made.     

Determination of 238Pu, 239+240Pu and 241Am in air filters

The aim of this work is to present the method for sequential plutonium and americium activity determination in air filters using chromatographic radionuclide separation and alpha spectrometry measurement. The developed method may be employed for the purposes of workplace monitoring and as an indicator of the need of introducing the individual monitoring as well as a useful complementation of individual monitoring. Basic parameters describing the developed method such as values of chemical recoveries and minimum detectable activities for plutonium and americium isotopes have been determined. Applied counting efficiency was obtained using Monte Carlo calculation method.

     

Isolation and alpha-particle spectrometric determination of238Pu and239,240Pu in sediments

A simple method is described for the isolation and determination of plutonium isotopes in sediments. The method involves leaching of sample with nitric acid and subsequent separation of plutonium on an anion-exchange column. Major matrix elements and several potential radiochemical interferences are removed during 8M HNO₃ sample loading on the column. Thorium is removed by thorough washing with 10M HCl. Plutonium (IV) is eluted with 4M HCl. Source for alpha-particle spectrometry is prepared by LaF₃ coprecipitation technique at which stage a complete separation from uranium(VI) is also achieved. The entire analytical procedure is completed in about two days.     

Determination of239,240Pu and241Am in environmental samples

An accurate and reliable method has been developed and routinely carried out for the sequential determination of^239,240Pu and²⁴¹Am in environmental samples. After suitable pretreatment.^239,240Pu and²⁴¹Am are separated from other elements by means of the anion exchange resin method. Americium-241 is purified by coprecipitation with calcium oxalate and then ion exchanged in mixed media of the mineral acid-methanol. In the analysis,²⁴²Pu (or²³⁶Pu) and²⁴⁴Cm are used as chemical yield monitors. The recoveries of the yield monitors in the analyses of some kinds of environmental samples were 7080% for plutonium and 7686% for curium. The concentration of^239,240Pu in the coastal sea water were 7.022 Bq/l and that of²⁴¹Am was 1.26.3 Bq/l. The mean concentrations of^239,240Pu in the edible parts of the marine products ranged from 0.22 to 7.4 mBq/kg · fresh and those of²⁴¹Am ranged from 0.11 to 2.6 mBq/kg · fresh.