Stefania Gaudino

Radioecological survey at selected sites hit by depleted uranium ammunitions during the 1999 Kosovo conflict.

A field study, organised, coordinated and conducted under the responsibility of the United Nations Environment Programme (UNEP), took place in Kosovo in November 2000 to evaluate the level of depleted uranium (DU) released into the environment by the use of DU ammunition during the 1999 conflict. Representatives of six different scientific organisations took part in the mission and a total of approximately 350 samples were collected. During this field mission, the Italian National Environmental Protection Agency (ANPA) collected water, soil, lichen and tree bark samples from different sites. The samples were analysed by alpha-spectroscopy and in some cases by inductively coupled plasma-source mass spectrometry (ICP-MS). The 234U/238U and 235U/238U activity concentration ratios were used to distinguish natural from anthropogenic uranium. This paper reports the results obtained on these samples. All water samples had very low concentrations of uranium (much below the average concentration of drinking water in Europe). The surface soil samples showed a very large variability in uranium activity concentration, namely from approximately 20 Bq kg(-1) (environmental natural uranium) to approximately 2.3 x 10(5) Bq kg(-1) (approximately 18000 mg kg(-1) of depleted uranium), with concentrations above environmental levels always due to DU. The uranium isotope measurements refer to soil samples collected at places where DU ammunition had been fired; this variability indicates that the impact of DU ammunitions is very site-specific, reflecting both the physical conditions at the time of the impact of the DU ammunition and any physical and chemical alteration which occurred since then. The results on tree barks and lichens indicated the presence of DU in all cases, showing their usefulness as sensitive qualitative bio-indicators for the presence of DU dusts or aerosols formed at the time the DU ammunition had hit a hard target. This result is particularly interesting considering that at some sites, which had been hit by DU ammunition, no DU ground contamination could be detected.

Determination of uranium isotopes in environmental samples by alpha-spectrometry

A new and accurate method for the determination of uranium isotopes (238U, 234U and 235U) in environmental samples by alpha-spectrometry has been developed. Uranium is preconcentrated from filtered water samples by coprecipitation with iron(III) hydroxide at pH 9-10 using an ammonia solution and the precipitate is dissolved in HNO3 and mineralized with H2O2 and HF; uranium in biological samples is ashed at 600 °C, leached with Na2CO3 solution and mineralised with HNO3, HF and H2O2; uranium in soil samples is fused with Na2CO3 and Na2O2 at 600 °C and leached with HCl, HNO3 and HF. The mineralized or leaching solution in 2M HNO3 is passed through a Microthene-TOPO (tri-octyl-phosphine oxide) column; after washing, uranium is directly eluted into a cell with ammonium oxalate solution, electrodeposited on a stainless steel disk and measured by alpha-spectrometry. The lower limits of detection of the method is 0.37 Bq.kg-1 (soil) and 0.22 mBq.l-1 (water) for 238U and 234U and 0.038 Bq.kg-1 (soil) and 0.022 mBq.l-1 (water) for 235U if 0.5 g of soil and 1 litre of water are analyzed. Five reference materials supplied by the IAEA have been analyzed and reliable results are obtained. Sample analyses show that, the 238U, 234U and 235U concentrations are in the ranges of 0.30-103, 0.49-135 and 0.02-4.82 mBq.l-1 in waters, of 1.01-7.14, 0.85-7.69 and 0.04-0.32 Bq.kg-1 in mosses and lichens, and of 25.6-53.1, 26.4-53.8 and 1.18-2.48 Bq.kg-1 in sediments. The average uranium yields for waters, mosses, lichens and sediments are 74.5±9.0%, 80.5±8.3%, 77.8±4.9% and 89.4±9.7%, respectively.

Concentration, distribution and characteristics of depleted uranium (DU) in the Kosovo ecosystem: A comparison with the uranium behavior in the environment uncontaminated by DU

The smear samples of the penetrator were analyzed for the determination of the uranium composition. The obtained relative composition (m/m) of uranium isotopes in all the smear samples is in the range of 99.76-99.78% for 238U, 0.000659-0.000696% for 234U, 0.213-0.234% for 235U, and 0.00274-0.00328% for 236U, showing characteristics of depleted uranium (DU). The uranium concentrations in Kosovo soil and water samples as well as biological samples were investigated. It was found that the uranium concentrations in the Kosovo soil samples are in the range of 11.3-2.26·105 Bq·kg-1 for 238U, 10.3-3.01·104 Bq·kg-1 for 234U, 0.60-3251 Bq·kg-1 for 235U, and £0.019-1309 Bq·kg-1 for 236U. The obtained activity ratios are in the range of 0.112-1.086 for 234U/238U, 0.0123-0.1144 for 235U/238U, and 0-0.0078 for 236U/238U, indicating the presence of DU in about 77% of the surface soil samples. At a specific site, the DU inventory in the surface soil is about 140 mg·cm-2, which is 1.68·106 times higher as the estimated mean DU dispersion rate in the region. The uranium concentrations in Kosovo lichen, mushroom, bark, etc., are in the range of 1.97-4.06·104 Bq·kg-1 for 238U, 0.48-5158 Bq·kg-1 for 234U, 0.032-617 Bq·kg-1 for 235U, and £0.019-235 Bq·kg-1 for 236U with mean activity ratios of 0.325±0.0223 for 234U/238U, of 0.0238±0.0122 for 235U/238U, and 0.0034±0.0028 for +U/238U, indicating the presence of DU in the entire sample. On the contrary, the uranium concentrations in Kosovo water samples are low, compared with the water samples collected in central Italy, indicating the presence of negligible amount of DU. The uranium isotopes in Kosovo waters do not constitute a risk of health at the present time.

Accumulation of nitrogen and changes in assimilation pigments of lichens transplanted in an agricultural area

The results of a survey aimed at testing the hypothesis that the lichen Evernia prunastri, when transplanted in an agricultural area with high atmospheric NH3 concentrations, would respond to NH3 air pollution accumulating nitrogen in its thalli and showing changes in the concentration of assimilation pigments are presented. The results confirmed the hypothesis and showed that all lichen transplants accumulated nitrogen, suggesting that besides the release of atmospheric ammonia by animal stockfarms, the use of N-based fertilizers and the deposition of N-rich dust also may contribute to the high nitrogen availability to lichens in the study area. The result indicated that in the study area both the critical level of NH3 and the critical load of N for lichens are exceeded and physiological damage is to be expected in sensitive species. The results of assimilation pigments in E. prunastri, with a decrease in the concentration of chlorophylls a and b and carotenoids, as well as chlorophyll degradation to phaeophytin, confirmed this hypothesis. However, owing to the limited data set and pending further studies, these conclusions should be considered as limited to the study area.