Umberto Sansone

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.

210Pb and 210Po determination in environmental samples

Sequential separation of 210Pb and 21OPo in environmental samples allows the determination of these naturally occurring radionuclides with good chemical yields and low detection limits. After sample mineralization, part of the leaching solution is used for 210Po determination which does not require any further treatment and essentially quantitative recoveries are obtained, using a standard 209Po tracer. The remaining part of the leaching solution is used for 210Pb determination. Starting from 3 g sediment (30 l water), the lower limits of detection of the method are 1.4 Bq kg(-1) (0.14 mBq l(-1)) for 210Pb and 0.25 Bq kg(-1) (0.016 mBq l(-1)) for 21OPo. The procedure has been checked by analysing two certified reference materials, supplied by IAEA, and reliable results have been obtained.

210Pb and 210Po concentrations in the Venice lagoon ecosystem (Italy) and the potential radiological impact to the local public and environment

In order to evaluate the possible radiological impact to the local public and environment from a phosphogypsum stockpile, 210Po and 210Pb concentrations in river water, lagoon water, suspended matter, superficial sediment, algae and bivalves samples collected in Venice lagoon area have been investigated. The results show that the mean 210Po and 210Pb concentrations in river water are 1.42±0.36 mBq.l-1 and 1.46±0.39 mBq.l-1 with a mean 210Po/210Pb ratio of 0.98±0.17 and about 60% of them are associated with the particulate; 210Po and 210Pb contribution from the phosphogypsum stockpile to the river water is negligible. Higher 210Po (2.61-5.67 mBq.l-1) and 210Pb (1.31-3.62 mBq.l-1) concentrations in the lagoon waters have been observed if compared with the literature values. About 60% of 210Po and 210Pb are found in the soluble form with a mean 210Po/210Pb ratio of 1.79±1.47. 210Po and 210Pb concentrations in 28 out 37 sediment samples ranged from 26 to 45 Bq.kg-1 (dry weight), only 9 sediments with 210Po and 210Pb concentrations greater than 45 Bq.kg-1 are found and most of them are located 1-4 km near the phosphogypsum stockpile. The elevated 210Po and 210Pb concentrations in the sediments may be due to the contamination from the phosphogypsum stockpile. The mean 210Po/210Pb ratio (0.986±0.049) in the sediments shows that 210Po and 210Pb exist in nearly secular equilibrium. 210Po and 210Pb concentrations in algae vary with different species. The mean 210Po and 210Pb concentrations in Gracilaria compress and Ulva laetevirens which show a similar behavior, are 3.18±1.23 Bq.kg-1 and 2.42±1.26 Bq.kg-1 (fresh weight), respectively, with a mean 210Po/210Pb ratio of 1.45±0.34. The mean concentration factors with respect to the filtered water are 1096±424 for 210Po and 1299±680 for 210Pb. The mean 210Po and 210Pb concentrations in the soft part of Mytilus edulis are 23.2±9.7 Bq.kg-1 and 0.537±0.203 Bq.kg-1 (fresh weight), respectively, with a mean 210Po/210Pb ratio of 43.6±10.0. The mean concentration factors with respect to the filtered water are 8006±3351 for 210Po and 290±109 for 210Pb, showing a very high accumulation effect for 210Po. The accumulation behaviors of Cerastoderma glaucum and Tapes philippinarum for 210Po are similar to Mytilus edulis, but that for 210Pb seems less effective, corresponding to a relatively higher 210Po/210Pb ratio. The estimated committed effective doses from 210Po for the individual local public through ingestion of bivalves are in the range of 0.050-0.231 mSv.y-1.

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.

137Cs and 90Sr in water and suspended particulate matter of the Dnieper River-Reservoirs System (Ukraine)

Fallout from the Chernobyl accident caused extensive contamination in the drainage basin of the Dnieper cascade (Ukraine). From 1986, a radiological monitoring system has been established along the Dnieper system of reservoirs. Samples of water were regularly collected in the rivers feeding the Kiev reservoir and in the inflows and outflows of the six large artificial reservoirs (Kiev, Kanev, Kremenchug, Dniprodzerdzin, Zaporozhie, Kakhovka) composing the Dnieper cascade system. Measurements of radiocaesium and radiostrontium made from 1987 to 1993 showed that the radioactive contamination of the rivers is considerably influenced by the hydrological conditions. As expected, the data revealed a close relationship between 90Sr concentration in water and river flow levels. 137Cs appears to be less dependent on surface hydrology. The reservoirs were found to act as sinks for radiocaesium with extensive accumulation recorded in the first reservoir. About 43% of the dissolved form of 90Sr that entered the Dnieper system from 1987 to 1993, reached the Black Sea.

Adhesion of water-borne particulates on freshwater biota.

The retention of suspended particles transported by river flow on surfaces of freshwater plants is a potentially important process in the contamination of aquatic biota. Field experiments have been performed to test the role of benthic algae (periphyton) in trapping inorganic suspended solids transported by the river water and to discriminate between the caesium content of periphyton caused by the adherence of inorganic solids and by the active uptake inside the organisms. The contribution of caesium of suspended solids adhering to biotic surfaces was estimated by determining the scandium content (scandium method). The scandium method was used because this element is geologically ubiquitous in soils and it is not taken up actively by plants and other organisms. The mass of suspended particles retained on the surfaces of microorganisms growing on submerged substrates were determined by comparing the scandium content of suspended material with that in algal communities. Neutron activation analysis was used as the analytical method for determination for both scandium, and caesium. The results indicate that the suspended particle fraction can contribute up to 80% of the caesium contamination of periphyton samples. Active caesium uptake and accumulation by aquatic biota represents the remaining 20% of the total caesium contamination.

Environmental mobility of radiocaesium in the Pripyat catchment, Ukraine/Belarus

Evidence from research in the Pripyat catchment, reviewed here, indicates that under the ecological conditions prevalent in this area, radiocaesium (137Cs) is highly mobile in both river water and poorly drained organic soils. Data collected at three different spatial and temporal scales demonstrate the effects of hydrological events on 137Cs mobility. During the period 1988–1994, 137Cs contamination in some poorly drained organic soils in the Pripyat catchment and in the milk from cows grazing on these soils are generally declining much faster than the radioactive half life. However, sharp increases in levels of 137Cs in both floodplain soils and milk to 2–3 times that observed immediately after the initial deposition have been measured immediately after summer floods. The processes causing these observed changes have not yet been fully explained but the sites where enhanced 137Cs mobility has been detected are clearly associated with the spatial patterns of organic soils and river flooding.

Behaviour of radiocaesium in a forest in the eastern Italian Alps

Abstract Radiocaesium behaviour has been studied in soil in a mixed forest located in the Carnic Alps (eastern part of Italy). Soil sampling along the vertical profile was carried out from October 1988 to October 1991. The results obtained show a very slow radiocaesium migration through the organic layers and indicate that after the fallout events, the radiocaesium isotopes deposited on the forest floor remain confined in the holorganic horizons for a long time.

Combining and reporting analytical results

Preface Environmental Metrology: the Italian Approach Comparability and Quality of Experimental Data Under Different Quality Systems The Role of Traceability in Sustainable Development - the UNIDO Approach Combination of Results from Several Measurements - An Everlasting Problem Quality Assurance of Chemical Measurements - Metrological or Management Effort Metrological Characteristics of the Conventional Measurement Scales for Hydrogen and Oxygen Stable Isotope Amount Ratios - The ?-Scales Experience with Metrological Traceability and Measurement Uncertainty in Clinical Chemistry Traceability of pH in a Metrological Context Determination of PCBs in Organic Solutions: An Example of Traceability Chain Quality Control of pH Measurements Considering Activity and Concentration Scales - Uncertainty Budget of Primary and Secondary Apparatuses Metrology in Complex Situations: Experiences with Thermodynamic Data Some Traceability Problems in Analytical Assays of interest in Thermal Metrology Developments in Uncertainty Evaluation: The Activity of JCGM/WG1 How to Combine Results Having Stated Uncertainties: To MU or Not to MU? Uncertainty and Traceability - The View of the Analytical Chemist Propagating Non-normally Distributed Uncertainty - The Ljungskile Code A Systematic Approach in the Evaluation of Uncertainty in Analytical Chemistry - Application to ICP-AES Analysis Self-Referring Procedure for the Full Cell Calibration of a Dynamic Gas Devider Investigation of Uncertainty Related to Measurement of Particulate Organic Pollutants Micronucleus Test in Fish Peripheral Erythrocytes - Variability in the Microscope Scoring Evaluation of intrinsic Uncertainty in the k0-NAA Reporting of Uncertainty in Environmental Monitoring of Radionuclides The Use of Reference Materials in International Reference Measurement Systems and for Comparison of Analytical Data The CSM Approach to the Calculation of the Uncertainty in XRF Analysis of Low- and High-Alloyed Steels Comparison of Different Approaches to Evaluate Proficiency Test Data Distribution of Proficiency Testing Results and Their Comparability Inter-Laboratory Comparison: the APAT Approach Proficiency Testing in the Biomedical Field - from Definitions of Targets to Use of Data from End-Users Measurement Uncertainty Its Role in Proficiency Testing Scheme - Case Study ILC Waste Water The Proficiency Testing of Laboratories: A First Approach to Implement Bayesian Methods in the Assessment of Performance The En, Uscore, and Accuracy Parameters - A Topic to Debate Collaborative Study for Pesticides Residues Determination in Water Samples (Method 5060 APAT-IRSA CNR) - Project 4b L. 93/01 Gross / Measurements in Drinking Waters by Liquid Scintillation Technique: Validation and interlaboratory Comparison Data Improvement of a Radiochemical Laboratory Through Fourteen Years Participation in a Intercomparison Program