Alpha-recoil atoms of plutonium in the environment

The -recoil effect of²³⁹Pu has been observed in environmental samples and theN ₅ ^P /N₅ ratio in these samples has been calculated. This ratio in atmospheric samples is in the range between 10^–5 and 10^–4 (atom/atom). For other contemporary terrestrial samples it is in the range between 10^–7 and 10^–6 (atom/atom), while that of uranium mineral is about 10^–10 (atom/atom). The results further explain the radioactive fallout contamination of our environment by uranium and plutonium isotopes.     

Luminescent determination of neptunium and plutonium in the environment

The preparation of^99mTc-complexes with nine derivatives of (4R)-1,3-thiazolidine-4-carboxylic acid over a broad pH range is described. The labeling efficiency of all compounds was checked by paper- and thin layer chromatography. Paper electrophoresis and gel chromatography indicated the presence of two types of^99mTc-complexes differing in charge and molecular size. Preliminary results of the biodistribution of anionic complexes in mice are given. The structure of both types of the Tc-complexes is also discussed.     

Regional distribution of Chernobyl-derived plutonium deposition in Finland

The Chernobyl nuclear power plant accident in April 1986 caused a widely spread plume of radionuclides containing, amongst other materials, plutonium isotopes. The regional deposition of these nuclides in Finland has been assessed, based on samples of lichen, peat, precipitation, surface soil and grass. Unlike the deposition of transuranium elements from the weapons tests in the 1950"s and the 1960"s, the deposition in Finland from the Chernobyl accident was very unevenly distributed. Even then, the Chernobyl-derived deposition of ^239,240Pu in the most contaminated regions of Finland was only around 10% of the global fallout from weapons tests. The total amount of ^239,240Pu deposited in Finland was 1^.10¹¹ Bq (»25 g), i.e., approximately half of a percent of the activity deposited in the 1950"s and the 1960"s. In addition to the alpha-emitting Pu isotopes, the Chernobyl plume also contained a significant amount of the beta-emitting ²⁴¹Pu, which is the precursor of the long-lived alpha-emitter ²⁴¹Am. The highest plutonium deposition values were found in a relatively narrow swath from the southwestern coast of Finland northeastwards across the country. This is related to the calculated route of the air parcel trajectory associated with the initial explosion of the Chernobyl reactor. The high deposition values found in the northeastern part of the plume route over Finland can be attributed to the simultaneous occurrence of precipitation. The relatively high plutonium deposition in the southwestern part of Finland occurred, however, without concurrent precipitation. This indicates that the plutonium was at least partly associated with relatively large particles having a substantial deposition velocity due to gravitational setting     

Rusty nails adsorb trace plutonium from the environment

Discarded rusty iron objects in the environment adsorb trace plutonium mobilized by oxygenated surface waters (e.g. rain, snow melt). Radiochemical and mass spectrometric analysis of the surface oxide coating of modest collections of rusty nails retrieved from remote locations provides a global fallout plutonium signal of up to 2 × 10¹⁰ atoms of ²³⁹Pu per sample. The median ²³⁹Pu measurement for 10 samples from five locations was 2.82 × 10⁹ atoms. The average ²⁴⁰Pu/²³⁹Pu atom ratio was 0.176 ± 0.012, consistent with the value accepted for global fallout.     

Behavior of plutonium isotopes in the marine environment of Enewetak atoll

There continue to be reports in the literature that suggest a difference in the behavior of^239+240Pu and²³⁸Pu in some aquatic environments. Plutonium isotopes have been measured in marine samples collected over 3 decades from Enewetak atoll, one of the sites in the Marshall Islands used by the United States between 1946 and 1958 to test nuclear devices. The plutonium isotopes originated from a variety of complex sources and could possibly coexist in this environment as different physical-chemical species. However results indicate little difference in the mobility and biological availability of^239+240Pu and²³⁸Pu.     

Effect of the oxidation number on estimates of a plutonium hydrolysis constant

Four new formulas for estimating the first hydrolysis constant of tetravalent plutonium are illustrated. They can be applied with or without an independent estimate of the Pu oxidation number.     

Geochemical association of plutonium in sediments of the Trombay coastal environment

Geochemical association of plutonium in the coastal environment of Trombay has been studied. A sequential leaching method was employed for chemical partitioning of plutonium in sediments. The results show that 95±15% of plutonium was extracted by different leaching reagents out of which 85±14% was associated with organic matter and hydrous oxide and 9±4% with residual fraction.The presence of significant fraction of Pu bound with organic matter of the sediment is an important factor in determining the extent to which an element becomes available to bottom feeding biota and so enters the aquatic food chain.     

Relationships between deposition of Chernobyl originating caesium and ruthenium radionuclides and rainfall in Ireland.

Deposition data for caesium and ruthenium radionuclides in Ireland as a result of the Chernobyl accident were obtained by high-resolution gamma-ray spectrometry of soil samples taken at 111 locations throughout the country. Investigation of the relationships between deposition and recorded rainfall in relevant periods enabled an assessment to be made of the activity concentration within the plume during the wash-out phase. Detailed surveys in two regions of the country enabled a comparison to be made of the relative deposition of ruthenium and caesium isotopes. No evidence was found to suggest any difference in wash-out ratios for the two ruthenium isotopes.     

The measurement of the isotopic composition of plutonium in an Irish Sea sediment by mass spectrometry

Samples from sediment cores, collected from a site close to the Sellafield outfall and dated using conventional - and -spectrometry, have been analysed using Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and Thermal Ionisation Mass Spectrometry (TIMS). This has provided information on the isotopic composition of plutonium in the liquid discharges from Sellafield; such information is not available using conventional -spectrometry alone. There was very good agreement between the²⁴⁰Pu/²³⁹Pu ratios obtained by the two MS methods. More recent discharges have been characterised by a progressive decrease in the relative proportion of²³⁹Pu.     

Study on the behavior of129I in the terrestrial environment

Transfer parameters for dose assessment such as deposition velocity (V _g), fraction of directly deposited on plants to the edible parts (r) and transfer factors (B _iv) have been evaluated. Deposition velocity under drying and wet conditions was evaluated about 0.8 cm/s. Fraction of directly deposited on plants and transfer factors in plants showed a lognormal distribution. Geometric means of fraction of deposited in rice, leafy vegetable and grass were <9·10^–3, 0.2 and about 9·10^–2, respectively. Geometric mean of the transfer factor in leafy vegetable was about 3·10^–2. These results were compared with the parameters given in the US NRC Regulatory Guide and previous literature values. The results showed that the fraction of directly deposited on plants were smaller than the recommended value in the NRC Regulatory Guide. They also showed that the deposition velocity and transfer factors were almost similar to the results reported in the literature.     

Processes driving the degradation of polybrominated diphenyl ethers in terrestrial environment

Polybrominated diphenyl ethers (PBDEs), a class of brominated flame retardants, have gained the attention of many researchers due to their persistence in various environmental matrices. Their usage in numerous consumer products has lent credence to their ability to retard flammable gas formation and brought attention to their ubiquitous occurrence in the environment. PBDEs have been described as endocrine-disrupting chemicals because of their interference with the endocrine system in aquatic and terrestrial animals. In spite of the progress in research over the decades on PBDEs, a full understanding of the environmental behavior and fate of this contaminant is still elusive. Therefore, terrestrial contamination of PBDEs has been evaluated in conjunction with their levels of toxicity, transformation, and transport in various environmental compartments. This review provides a wider perspective of the behavior of PBDEs in the terrestrial environment. Through examining the numerous studies on the environmental contamination of PBDEs, a number of mounting concerns and data gaps have been identified. Numerous methodologies have been discussed including adsorption, catalytic, photocatalytic, electrocatalytic, photo-electrocatalytic, aerobic, and anaerobic degradation. The comparative PBDE degradation analysis suggests that the oxidative degradation pathway is the most appropriate way of wastewater treatment while the role of other soil ingredients on subsurface treatments is still under investigation.     

Is plutonium really a threat to man and his environment?

Plutonium is a vital source of energy. The importance of plutonium as a source of energy can easily be understood by a simple fact that the amount of energy produced from one gram of plutonium is equal to the energy produced from 100 g of uranium and/or one ton of oil. Plutonium poses little or no problem as a high level waste. This can be predicted from our earlier studies on Th in man which has indicated that the general population of the United States exposed to insoluble Th throughout the life times accumulates the amount of Th contained in 1–6 g of soil. Furthermore, the vitrification process can prevent the translocation of Pu into the environment from the waste storage site quite effectively. Plutonium is a great asset to the human race only if they are civilized and use this great element for their prosperity as a source of energy. However, if the people and/or their leaders become barbaric, inhumane, crazy and misguided, then Pu could be the greatest threat to the survival of human race. Therefore, man himself could become the greatest threat to the human race.     

Investigations of radiocaesium in the natural terrestrial environment in Norway following the Chernobyl accident.

Radioactive fallout from the Chernobyl accident affected parts of central Norway to a considerable extent, in particular the 134Cs+137Cs deposition had a significant impact on the natural environment. When this became apparent, a comprehensive radioecological research programme was initiated in order to study the behaviour of radiocaesium in boreal and alpine ecosystems, with emphasis on food-chains leading to exposure of species used for human consumption, i.e., reindeer and freshwater fish. In this paper results from the terrestrial part of this research programme during the period 1986-1990 are presented. The work was mainly confined to the mountain areas of Dovre and Rondane. Parallel studies were performed in eutrophic and strongly oligotrophic communities. The influence of local variations in topography and microclimate on the observed radiocaesium levels in topsoils, lichens and vascular plants was studied in detail. Currently a significant re-distribution of radiocaesium from the originally strongly exposed surfaces to those that were less exposed is observed. In the soil, radiocaesium is strongly retained in the litter and raw humus layers. Current levels in lichens are 1-2 orders of magnitude higher than in vascular plants. This strongly affects the seasonal variation of radiocaesium in reindeer, showing winter maxima of about 5 times higher than the August levels. The radiocaesium levels in reindeer showed a decline of approximately a factor of 3 during the period 1987-1990. Other animal species studied in the programme exhibited substantially lower radiocaesium levels than reindeer, but a considerable interspecies variation was observed.     

Separation and determination of radioactive caesium in milk

A method is given for the separation and determination of radiocaesium in fluid milk. Caesium is separated from organic material and interfering ions by passage of the milk sample through a cation-exchanger in the lithium form. It is eluted from this column with 6M hydrochloric acid. Two methods are given for the recovery of radiocaesium from the eluate. It may be precipitated with silico-tungstic acid and then converted into caesium perchlorate for counting or weighing. Alternatively, the eluate is passed through a small column of ammonium phosphomolybdate, which quantitatively sorbs the radiocaesium, the activity of which is determined by putting the column in a well-type scintillation counter and measuring the activity. Approximately 90% of the radiocaesium is recovered.     

Surprising coordination for plutonium in the first plutonium(III) borate

The first plutonium(III) borate, Pu(2)[B(12)O(18)(OH)(4)Br(2)(H(2)O)(3)]·0.5H(2)O, has been prepared by reacting plutonium(III) with molten boric acid under strictly anaerobic conditions. This compound contains a three-dimensional polyborate network with triangular holes that house the plutonium(III) sites. The plutonium sites in this compound are 9- and 10-coordinate and display atypical geometries.     

The caesium oxygen interactions in the crystalline solids

Through the study of the Cs-O bonds registered in the literature one observes that:

(i)

the bond lengths range from 2.46 to 3.60 Å;

(ii)

the preferential coordination numbers adopted by the caesium ions are 8, 9 and 10 but values from 1 to 12 also exist;

(iii)

the average bond lengths increase with the coordination (CN) of the caesium ions with the following values: 2.714 Å (CN=1), 2.98 Å (CN=2), 3.057 Å (CN=3), 3.104 Å (CN=4), 3.149 Å (CN=5), 3.188 Å (CN=6), 3.224 Å (CN=7), 3.245 Å (CN=8), 3.261 Å (CN=9), 3.269 Å (CN=10), 3.293 Å (CN=11) and 3.323 Å (CN=12).

A new R_ij=2.469 constant is determined with all the caesium coordination polyhedra to compute electrostatic bond valence sums.The U_eq values of caesium in crystal structure are about 0.03 and generally less than 0.06 similar to those of the oxygen atoms and often bigger.     

Redox determination of uranium in presence of plutonium in low phosphoric acid medium and the recovery of plutonium

Quantitative determination of uranium in (U, Pu)O₂ fuels is usually done by the DAVIES-GRAY method. High concentrations of phosphoric acid in the analytical waste generated by this method make the revocery of plutonium rather complex. Studies on the recovery of plutonium from nitric acid medium containing different concentrations of H₃PO₄ by conventional anion-exchange procedure reveal that more than 90% of the plutonium can be easily recovered when the phosphoric acid concentration is less than 0.5 M in the solution. A method was developed for the determination of uranium in the presence of plutonium, which involves the reduction of U(VI) to U(IV) by Fe(II) in a medium of 3.5M H₃PO₄ +4.5M H₂SO₄ instead of 10–11M H₃PO₄ so as to have the H₃PO₄ concentration 0.6M in the waste. A number of determinations of uranium in UO₂(NO₃)₂ working standard solutions and (U, Pu) synthetic solutions with uranium at the 3–7 mg level were carried out by this method. The precision obtained was better than ±0.2% and the accuracy was also within the precision limits. The resulting analytical waste generated was directly subjected to anion exchange separation for the recovery of plutonium which was found to be more than 90%.     

Determination of uranium and plutonium in plutonium based fuels by sequential amperometric titration

A method is described for the sequential determination of uranium and plutonium in plutonium bearing fuel materials. Uranium and plutonium are reduced to U(IV) and Pu(III) with titanous chloride and then titrated with dichromate to two end points which are detected amperometrically using two polarized platinum electrodes. Uranium-plutonium solutions of known concentrations containing plutonium in the proportions of 4, 30, 50, and 70% were analyzed with precisions better than 0.3%, maintaining the amounts of plutonium per aliquot in the range of 2–10 mg. No significant bias could be detected. Several samples of (U, Pu)O₂ and (U, Pu)C were analyzed by this procedure. The effects of iron, fluoride, oxalic acid and mellitic acid on the method were also studied.