Sylwia Błażej

137Cs and 40K in fruiting bodies of different fungal species collected in a single forest in southern Poland.

Fruiting bodies of fungi belonging to more than 70 species were collected within a few thousand square meter area of one forest during 2006 and 2007. The soil profile was collected to check the cumulative deposition of (137)Cs, which was relatively high, equal to 64 +/- 2 kBq/m(2) (calculated for October 2006). The majority of this activity was in the first 6 cm. Fruitbodies were analyzed for radiocesium and (40)K by means of gamma-spectrometry. The highest (137)Cs activity was 54.1 +/- 0.7 kBq/kg (dry weight) for a sample of Lactarius helvus collected in 2006. The results for 2006 were higher than those for 2007. In a few cases the traces of short-lived (T(1/2) = 2.06 a) (134)Cs were still found in samples. The importance of mycorrhizal fungi for radiocesium accumulation is confirmed. The differences in activity among the species are discussed in relation to observations and predictions from previous studies, where the change in relative accumulation between fruiting bodies of different species was at least partially explained by the differences in the depth of the mycelium localization in a litter/soil system. It is concluded that in some cases, such as Boletus edulis and Xerocomus badius, this prediction is fulfilled and therefore this explanation confirmed.

Substituent Effects on the Electrophilic Activity of Nitroarenes in Reactions with Carbanions

The effect on electrophilic activity of substituents located para, ortho, and meta to the nitro group of nitrobenzenes was determined by using vicarious nucleophilic substitution of hydrogen (VNS) with the carbanion of chloromethyl phenyl sulfone (1) as the model process. Values for the relative activities of substituted nitroarenes are given relative to nitrobenzene, which was taken as the standard. This process was chosen as a model reaction because it meets key criteria, such as the wide range of substituents that can be present on the nitrobenzene ring, a low sensitivity to steric hindrance, and in particular the possibility of ensuring conditions in which the overall relative rates of reaction in competitive experiments are equal to the relative rates of nucleophilic addition. The values of relative rates of addition, which were taken to be a measure of electrophilic activity, were determined by competitive experiments in which pairs of nitroarenes competed for the VNS reaction with carbanion of 1. A comprehensive set of data for effects of substituents on the electrophilic activity of nitroarenes is presented for the first time.

Reactions of Nitroheteroarenes with Carbanions : Bridging Aromatic, Heteroaromatic, and Vinylic Electrophilicity

The relative rate constants for the vicarious nucleophilic substitution (VNS) of the anion of chloromethyl phenyl sulfone (1-) with a variety of nitroheteroarenes, for example, nitropyridines, nitropyrroles, nitroimidazoles, 2-nitrothiophene, and 4-nitropyrazole, have been determined by competition experiments. It was shown that nitropyridines are approximately four orders of magnitude more reactive than nitrobenzene. Among the five-membered heterocycles 2-nitrothiophene is the most active followed by nitroimidazoles and 4-nitropyrazole. Nitropyrroles are the least electrophilic nitroheteroarenes with reactivities comparable to nitrobenzene. Quantum chemically calculated methyl anion affinities (B3LYP/6-311G(d,p)//B3LYP/6-31G(d)) of the nitroarenes correlated only moderately with the partial relative rate constants. The correlation of these activities with the LUMO energies of nitroarenes is even worse. By measuring the second-order rate constants of the addition of 1- to nitroarenes and to diethyl arylidenemalonates 10, it was possible to link the electrophilic reactivities of nitroheteroarenes with the comprehensive electrophilicity scale based on the linear-free-energy-relationship log k(20 degrees C)=s(N+E).

137Cs, 40K, 238Pu, 239+240Pu and 90Sr in biological samples from King George Island (Southern Shetlands) in Antarctica

There are few data reported on radionuclide contamination in Antarctica. The aim of this paper is to report 137Cs, 90Sr and 238,239+240Pu and 40K activity concentrations measured in biological samples collected from King George Island (Southern Shetlands, Antarctica), mostly during 2001–2002. The samples included: bones, eggshells and feathers of penguin Pygoscelis papua, bones and feathers of petrel Daption capense, bones and fur of seal Mirounga leonina, algae Himantothallus grandifolius, Desmarestia anceps and Cystosphaera jacquinotii, fish Notothenia corriceps, sea invertebrates Amphipoda, shells of limpet Nacella concina, lichen Usnea aurantiaco-atra, vascular plants Deschampsia antarctica and Colobanthus quitensis, fungi Omphalina pyxidata, moss Sanionia uncinata and soil. The results show a large variation in some activity concentrations. Samples from the marine environment had lower contamination levels than those from terrestrial ecosystems. The highest activity concentrations for all radionuclides were found in lichen and, to a lesser extent, in mosses, probably because lichens take up atmospheric pollutants and retain them. The only significant correlation (except for that expected between 238Pu and 239+240Pu) was noted for moss and lichen samples between plutonium and 90Sr. A tendency to a slow decrease with time seems to be occurring. Analyses of the activity ratios show varying fractionation between various radionuclides in different organisms. Algae were relatively more highly contaminated with plutonium and radiostrontium, and depleted with radiocesium. Feathers had the lowest plutonium concentrations. Radiostrontium and, to a lesser extent, Pu accumulated in bones. The present low intensity of fallout in Antarctic has a lower 238Pu/239+240Pu activity ratio than that expected for global fallout.

Plutonium, 137Cs and 90Sr in selected invertebrates from some areas around Chernobyl nuclear power plant.

Results are presented for (137)Cs, (90)Sr and plutonium activity concentrations in more than 20 samples of terrestrial invertebrates, including species of beetles, ants, spiders and millipedes, collected in the highly contaminated area of the Chernobyl exclusion zone. The majority of samples were collected in Belarus, with some also collected in the Ukraine. Three other samples were collected in an area of lower contamination. Results show that seven samples exceed an activity concentration of 100 kBq/kg (ash weight--a.w.) for (137)Cs. The maximum activity concentration for this isotope was 1.52+/-0.08 MBq/kg (a.w.) determined in ants (Formica cynerea). Seven results for (90)Sr exceeded 100 kBq/kg (a.w.), mostly for millipedes. Relatively high plutonium activity concentrations were found in some ants and earth-boring dung beetles. Analyses of activity ratios showed differences in transfer of radionuclides between species. To reveal the correlation structure of the multivariate data set, the Partial Least-Squares method (PLS) was used. Results of the PLS model suggest that high radiocesium activity concentrations in animal bodies can be expected mainly for relatively small creatures living on the litter surface. In contrast, high strontium activity concentrations can be expected for creatures which conduct their lives within litter, having mixed trophic habits and a moderate lifespan. No clear conclusions could be made for plutonium.

Traces of DU in samples of environmental bio-monitors (non-flowering plants, fungi) and soil from target sites of the Western Balkan region

This paper reports results of gamma and alpha spectrometric measurements for mosses, lichens, fungi and soil samples from areas in the Balkans targeted by depleted uranium (DU). Samples were collected in 2002 and 2003 in the vicinity of several villages, principally Han Pijesak (Bosnia and Herzegovina, hit by DU in 1995) and Bratoselce (South Serbia, hit by DU in 1999) and in lesser numbers from Gornja Stubla, Kosovo (which is identified as a high natural radon/thoron area) and Presevo close to the Kosovo border. In the course of gamma spectrometric measurements some results suggested samples with unusual high uranium contents which might be considered to be a signature for the presence of DU, although many samples had very high detection limits. Alpha spectrometric measurements directly proved the presence of DU for five samples, all from directly targeted places. These were samples of mosses, lichens and soil. For some samples homogeneity tests were applied which showed a rather even distribution of DU in these samples. No trace of DU was found in any sample from a dwelling.

Plutonium traces in atmospheric precipitation and in aerosols from Krakow and Bialystok

Abstract The appearance of plutonium isotopes in the environment was connected with the human activity, mainly: nuclear weapon tests (global fallout), nuclear accident in Chernobyl (1986), disintegration of satellite SNAP 9 (1963) and releases from nuclear reprocessing factories. At present, the concentration of plutonium in the atmosphere is very small but still observable. The aim of the study is to report and to discuss the results of plutonium alpha-emitters determination from sampling aerosols in air (Krakow 1990–1998, 2001–2002 and Bialystok 1996–1998, 2001) and in precipitation (Krakow 2005–2006). Plutonium activity concentration in air samples (in Krakow and Bialystok) varied in range: 0.22±0.04 nBq/m3 to 17.1±1.3 nBq/m3 for 239+240Pu and 0.033±0.018 nBq/m3 to 2.54±0.22 nBq/m3 for 238Pu and deposition of atmospheric precipitation (Krakow): from 0.041±0.011 mBq/m2 to 2.81±0.24 mBq/m2 for 239+240Pu and for 238Pu below 1.29±0.45 mBq/m2. One of the mechanisms responsible for the airborne plutonium is resuspension but on the other hand the main source of plutonium in the air seems to be marines aerosols from North See. This new hypothesis will be checked during the future research. The most interesting finding is the seasonal variation of plutonium air concentration. The conclusion from calculated ratio of plutonium isotopes (238Pu/239+240Pu) is that they are usually not typical for the global fallout.