U and Th in some brown coals of Serbia and Montenegro and their environmental impact

GOAL, SCOPE AND BACKGROUND: The objective of this paper is to determine and compare the concentrations of U and Th in soft to hard brown (lignite to sub-bituminous) coals of Serbia and Montenegro. It also presents comparison of the obtained data on U and Th concentrations with the published data on coals located in some other countries of the world. Almost the whole coal production of Serbia and Montenegro is used as feed coals for combustion in thermal power plants. METHODS: Channel samples from open pit and underground mines and core samples were collected for hard and soft brown coals. For the analysis the samples were decomposed using microwave technique. Obtained solutions containing U and Th were analyzed by inductively coupled plasma mass spectroscopy (ICP-MS) using NIST standards. RESULTS: Concentration of U from the investigated basins and the corresponding mine fields ranges within 0.60-70.10 mg/kg, 0.65-3.20 mg/kg, 0.95-6.59 mg/kg, 1.20-6.05 mg/kg, 0.80-6.66 mg/kg, 0.18-89.90 mg/kg, 0.19-4.14 mg/kg, and 0.28-3.52 mg/kg for the Kostolac, Kolubara, Krepoljin, Sjenica, Soko Banja, Bogovina East field, Senje-Resavica and Pljevlja basins, respectively. Concentration of Th ranges within 0.20-2.60 mg/kg, 0.84-6.57 mg/kg, 1.48-6.48 mg/kg, 0.12-2.71 mg/kg, 0.13-4.95 mg/kg, 0.14-3.48 mg/kg, 0.29-3.56 mg/kg, and 0.17-1.89 mg/kg for the Kostolac, Kolubara, Krepoljin, Sjenica, Soko Banja, Bogovina East field, Senje-Resavica and Pljevlja basins, respectively. DISCUSSION: Brown coal from Senje-Resavica, Kolubara, Kostolac and Pljevlja is characterized by low U concentration. Coals form the Krepoljin, Soko Banja and Sjenica basins have slightly higher U concentrations than the mentioned group. The highest concentration of U is characteristic for the coal from the Bogovina East field. Concentration of Th in coals from Serbia and Montenegro has proved to be low. Out of all investigated coal basins, only the coal from the Krepoljin and Kolubara basins has high concentration of Th. The hydrothermally altered rocks of the Timok dacite-andesite complex, representing the basement of the Bogovina basin, could be a potential source of U, especially at the bottom part of the Lower seam of the Bogovina East field. CONCLUSIONS: This study shows that brown coals in Serbia and Montenegro (soft to hard brown coals or lignite to sub-bituminous) contain low levels of U (5.30 mg/kg, average value and 2.10 mg/kg geometric mean value) and Th (1.80 mg/kg, average value and 1.12 mg/kg geometric mean value). There are some obvious differences in concentration of U and Th in coals from different basins in Serbia and Montenegro. The approximate value for U and Th release mainly from power plants was 644.33 t and 983.46 t, respectively within the period 1965-2000 for the studied mines in Serbia, and 23.76 t and 15.05 t for the Potrlica mine (Montenegro) within the period 1965-1997. RECOMMENDATIONS: The coals in Serbia and Montenegro show no identifiable unfavourable impact on the surrounding environment, due to low natural radioactive concentration of U and Th, but further investigations concerning human health should be performed. PERSPECTIVES: Preliminary research revealed that in some Serbian coals (and, particularly, parts of the coal seam) U and Th content are rather high. Such coals should be carefully studied, as well as U and Th concentrations in ash, fly ash, waste disposals, nearby soil and ground water. Further studies should include determination of the radioactivity of all these products, and estimation of possible health impact.     

Environmental tritium of the Danube basin in Yugoslavia

An overview of environmental distribution of tritium in the Danube basin in Yugoslavia during the period 1976-1990 is presented. Temporal and regional variations of environmental tritium in the Danube along its flow (1425-847 km from the confluence) and its tributaries (the Sava, the Tisa, the Velika Morava and the Timok) at various locations, as well as in alluvial groundwaters, are given. In Belgrade, monthly values of tritium in rainfall ranged from 1.1 to 18.3 Bq litre(-1), with a maximum in the late spring and early summer months. The half-life for decline in concentration was estimated as 8.3+/-1.0 years. The total amount of tritium deposited in the first 6 months during 1976-90 was 35% larger than in the second 6 months for the same period. Seasonal variations were noticeable in rivers and groundwaters, but these were greatly attenuated and smoothed for the latter. Tritium content in the monthly composite samples from the river in the Belgrade region varied between 2.5 and 18.2 Bq litre(-1) for the Danube and from 1.5 to 16.8 Bq litre(-1) for the Sava. The yearly mean values along the Danube and its tributaries ranged from 2.4 to 15.9 Bq litre(-1) with individual measurements 1.0-30.2 Bq litre(-1). The half-lives were between 6.9+/-1.7 for the Velika Morava and 9.4+/-0.9 for the Danube. Groundwaters, particularly ones in the Ranney wells, followed changes of tritium content in the rivers with a time lag from a few days to a month. During the period of observation, tritium content decreased in alluvial waters with half-lives from 9.9+/-1.6 (Belgrade area) to 7.3+/-1.8 (the Velika Morava).     

Kinetic sodium analyses in the crab Carcinus mediterraneus

Kinetic analyses were made of the stable sodium and radioactive sodium (²²Na) in some tissues of the crab Carcinus mediterraneus CSRN. Fast ²²Na outflux constant is increased in gills, hepatopancreas, hemolymph, digestive tract and muscles. In the reproductive organs the values of the sodium outflux constant are lower. The values of the fast outflux rates (t=20°C) of sodium amount, in the whole animal, to 22.5 M Na/g/h, in the hemolymph, to 69.3 M Na/g/h; the slow outflux rates have much lower values (0.02 to 0.13 M Na/g/h). Moulting crabs show a rate of sodium outflux 6 times greater than that of intermoulting individuals.     

Natural bitumens versus oil pollution in the Vlasina lake peat

Free and associated bitumens were isolated by sequential extraction from Vlasina lake peat (SE Serbia) and were investigated in order to differentiate between oil pollution and natural bitumens. Four peat samples were collected at different depths, on a peat island. Gas chromatographic (GC) and gas chromatography/mass spectrometry (GC/MS) analysis revealed the presence of three markedly different bitumen fractions. Here we show that the free bitumens are representing the native peat bitumens. The two associated bitumens are mainly the products of bacterial rework of organic substance, which were then trapped by two differing mechanisms. The bitumens characteristics and association features exclude a contribution of oil pollution.Selected article from the Regional Symposium on Chemistry and Environment Krusevac, Serbia, June 2003, organised by Dr. Branimir Jovancicevic.     

The influence of climate and soil properties on calcium nutrition and vitality of silver fir (Abies alba Mill.)

As a part of a broader research into the nutrition of silver fir (Abies alba Mill.), the variation of calcium concentrations was investigated in needles and soil in two subsequent, climatologically diverse years. Statistically significant differences between plots were determined in Ca concentrations in soils. Concentrations of Ca in needles were statistically different regarding plot, defoliation class, sampling date within the same year and also between years. Fir trees on acid-rock based soils had lower, often inadequate concentrations of Ca in needles; the opposite was true for trees growing on Ca-rich soils. Trees of lower vitality generally exhibited poor Ca nutrition. Drought in the second year of research caused poor absorption of Ca on all plots and in all defoliation classes, but the combined influence of climate and soil properties affected especially trees of low vitality on acid-rock based soils.     

The chemical and biogenotoxic characterization of organic xenobiotics in aquatic sediment materials 1. The application and comparison of chemically non-specific and biogenotoxic methods

The aim of this work was to evaluate the Ames assay and mixed function oxidase (MFO)-Induct Test used in parallel with chemical group tests (ECD fingerprint and PAH estimation) for the characterization of the organic pollution of water sediment materials. Sediment materials were collected from “clean” and relatively heavily polluted locations in the Middle Adriatic Sea, and from some locations in continental Croatia polluted with wastewaters from different enterprises. Characterization of the organic extracts of the sediment materials investigated was performed chemically using UV spectrofluorometry for the determination polyaromatic hydrocarbons (PAH) and gas chromatography for the determination of volatile EC detector sensitive materials. Genotoxic analysis of the extracts was performed using the MFO-Induct Test and mutagenicity testing using the Standard Plate Incorporation Test as described by Maron and Ames with Salmonella typhimurium TA 98. Measurement of the BaPMO enzyme activity in the livers of carp treated i.p. with total extracts of the sediment investigated confirmed that the methanol extracts generally contained more inducing matter than the petroleum ether extracts. Ames assay showed that for all the samples following the elimination of the sulfur, there was an increase in the number of revertants in comparison to the control number, which indicates that the samples contained mutagenic substances. The larger doses of extracts generally demonstrated cytotoxicity, as evidenced by a reduced number of spontaneous revertants in the Salmonella/Microsome Test. Investigation of the correlation of the chemical parameters with the biological parameter showed that the induction of BaPMO exhibited a statistically significant correlation with the level of the ECD fingerprint of the petroleum ether sediment extract.