Concentration and characteristics of depleted uranium in biological and water samples collected in Bosnia and Herzegovina

During Balkan conflicts in 1994-1995, depleted uranium (DU) ordnance was employed and was left in the battlefield. Health concern is related to the risk arising from contamination of the environment with DU penetrators and dust. In order to evaluate the impact of DU on the environment and population in Bosnia and Herzegovina, radiological survey of DU in biological and water samples were carried out over the period 12-24 October 2002. The uranium isotopic concentrations in biological samples collected in Bosnia and Herzegovina, mainly lichens, mosses and barks, were found to be in the range of 0.27-35.7 Bq kg(-1) for (238)U, 0.24-16.8 Bq kg(-1) for (234)U, and 0.02-1.11 Bq kg(-1) for (235)U, showing uranium levels to be higher than in the samples collected at the control site. Moreover, the (236)U in some of the samples was detectable. The isotopic ratios of (234)U/(238)U showed DU to be detectable in many biological samples at most sites examined, but in very low levels. The presence of DU in the biological samples was as a result of DU contamination in air. The uranium concentrations in water samples collected in Bosnia and Herzegovina were found to be in the range of 0.27-16.2 m Bq l(-1) for (238)U, 0.41-15.6 m Bq l(-1) for (234)U and 0.012-0.695 m Bq l(-1) for (235)U, and two water samples were observed to be DU positive; these values are much lower than those in mineral water found in central Italy and below the WHO guideline for public drinking water. From radiotoxicological point of view, at this moment there is no significant radiological risk related to these investigated sites in terms of possible DU contamination of water and/or plants.     

Isotopic composition and origin of uranium and plutonium in selected soil samples collected in Kosovo

Soil samples collected from locations in Kosovo where depleted uranium (DU) ammunition was expended during the 1999 Balkan conflict were analysed for uranium and plutonium isotopes content (234U, 235U, 236U, 238U, 238Pu, (239 + 240)Pu). The analyses were conducted using gamma spectrometry (235U, 238U), alpha spectrometry (238Pu, (239 + 240)Pu), inductively coupled plasma-mass spectrometry (ICP-MS) (234U, 235U, 236U, 238U) and accelerator mass spectrometry (AMS) (236U)). The results indicated that whenever the U concentration exceeded the normal environmental values (approximately 2 to 3 mg/kg) the increase was due to DU contamination. 236U was also present in the released DU at a constant ratio of 236U (mg/kg)/238U (mg/kg) = 2.6 x 10(-5), indicating that the DU used in the ammunition was from a batch that had been irradiated and then reprocessed. The plutonium concentration in the soil (undisturbed) was about 1 Bq/kg and, on the basis of the measured 238Pu/(239 + 240)Pu, could be entirely attributed to the fallout of the nuclear weapon tests of the 1960s (no appreciable contribution from DU).     

Depleted uranium particles in selected Kosovo samples

Selected soil samples, collected in Kosovo locations where DU ammunition was expended during the 1999 Balkan conflict, have been investigated by secondary ion mass spectrometry (SIMS), X-ray fluorescence imaging using a micro-beam (micro-XRF) and scanning electron microscopy equipped with an energy dispersive X-ray fluorescence detector (SEM-EDXRF), with the objective to test the suitability of these techniques to identify the presence of small DU particles and measure their size distribution and the 235U/238U isotopic ratio (SIMS). Although the results do not permit any legitimate extrapolation to all the sites hit by the DU rounds used during the conflict, they indicated that there can be "spots ' where hundreds of thousands of particles may be present in a few milligrams of DU contaminated soil. The particle size distribution showed that most of the DU particles were <5 microm in diameter and more than 50% of the particles had a diameter <1.5 microm. Knowledge on DU particles is needed as a basis for the assessment of the potential environmental and health impacts of military use of DU, since it provides information on possible re-suspension and inhalation.     

Oxidation states of uranium in depleted uranium particles from Kuwait

The oxidation states of uranium in depleted uranium (DU) particles were determined by synchrotron radiation based mu-XANES, applied to individual particles isolated from selected samples collected at different sites in Kuwait. Based on scanning electron microscopy with X-ray microanalysis prior to mu-XANES, DU particles ranging from submicrons to several hundred micrometers were observed. The median particle size depended on sources and sampling sites; small-sized particles (median 13 microm) were identified in swipes taken from the inside of DU penetrators holes in tanks and in sandy soil collected below DU penetrators, while larger particles (median 44 microm) were associated with fire in a DU ammunition storage facility. Furthermore, the (236)U/(235)U ratios obtained from accelerator mass spectrometry demonstrated that uranium in the DU particles originated from reprocessed fuel (about 10(-2) in DU from the ammunition facility, about 10(-3) for DU in swipes). Compared to well-defined standards, all investigated DU particles were oxidized. Uranium particles collected from swipes were characterized as UO(2), U(3)O(8) or a mixture of these oxidized forms, similar to that observed in DU affected areas in Kosovo. Uranium particles formed during fire in the DU ammunition facility were, however, present as oxidation state +5 and +6, with XANES spectra similar to solid uranyl standards. Environmental or health impact assessments for areas affected by DU munitions should therefore take into account the presence of respiratory UO(2), U(3)O(8) and even UO(3) particles, their corresponding weathering rates and the subsequent mobilisation of U from oxidized DU particles.     

Survey of natural and anthropogenic radioactivity in environmental samples from Yugoslavia

The radioactivity of 238U, 226Ra, 232Th, 40K and 137Cs in sediments, soil, turf and honey from Serbia and Kosovo (Yugoslavia) was measured using gamma and alpha spectrometry in order to estimate the radiation hazard from natural and man-made sources, as well as to compile a database for radioactivity levels in those regions. One sample, collected in the vicinity of a "depleted uranium" (DU) shell of the recent Balkan war, revealed a high 238U activity and a non-natural 235U/238U activity ratio, confirming therefore its anthropogenic origin. However, some other soil samples coming from characteristic DU craters did not show any characteristic level of radioactivity. The other sediment and turf samples taken all around the country show low radioactivity levels for all the isotopes here considered. With the aim of obtaining some indication about radioactivity migration in the food chain, several honey samples have been examined too. All samples show very low radioactivity content, often indistinguishable from natural background.     

Photon attenuation, natural radioactivity content and radon exhalation rate of building materials

High concentrations of natural radionuclides in building materials can result in high dose rates indoors, from both internal and external exposure. In dose calculations, the main radionuclides of interest are 226Ra, 232Th and 40K. Usually much attention is paid to 226Ra due to 222Rn exhalation and the subsequent internal exposure. Other radionuclides of the uranium series such as 238U and 210Pb, emitting low energy photons are not usually determined and an assumption of radioactive equilibrium is made. The above assumption is seldom checked mainly because of the difficulties in the gamma-spectroscopic analysis of low energy photons. For the determination of radionuclides emitting low-energy photons, in samples like building materials where intense self-absorption of the photons exists, a method for self-absorption correction has been developed. The method needs as input the linear attenuation coefficient mu for the material under analysis. This paper presents: 1. Correlations in the form mu = f(rho,E) developed for the estimation of the linear attenuation coefficient mu (cm(-1)), as a function of the material packing density p (g cm(-3)) and the photon energy E (keV), for building materials as well as other materials of environmental importance. 2. Gamma-spectroscopic analysis techniques used for the determination of 238U, 226Ra, 210Pb, 232Th and 40K in environmental samples, together with the results obtained from the analysis of building materials used in Greece, and industrial by-products used for the production of building materials. Among the techniques used, one is based on the direct determination of 226Ra and 235U from the analysis of the multiplet photopeak at approximarely186 keV. 3. Results from radon exhalation measurements of building materials such as cement and fly-ash and building structures conducted in the radon chambers in our Laboratory. Based on the above results, dosimetric calculations are also reported.     

Use of HPGe gamma-ray spectrometry to assess the isotopic compositiion of uranium in soils

Gamma-ray spectrometry was used to determine uranium activity and investigate the presence of depleted uranium in soil samples collected from camping sites of the Greek expeditionary force in Kosovo. Assessment of 238U concentrations was based on measurements of the 63.3 keV and 92.38 keV emissions of its first daughter nuclide, 234Th. To determine the isotopic ratio of 238U/235U, secular equilibrium along the two radioactive series was first ensured and thereby the contribution of 235U under the 186 keV peak was deduced. The uranium activity in the samples varied from 48 to 112 Bq kg(-1), whereas the activity ratio of 238U/235U averaged 23.1+/-4.3.     

Oxidation states of uranium in DU particles from Kosovo

The oxidation states of uranium contained in depleted uranium (DU) particles were determined by synchrotron radiation based micro-XANES, applied to individual particles in soil samples collected at Ceja Mountain, Kosovo. Based on scanning electron microscopy (SEM) with XRMA prior to micro-XANES, DU particles ranging from submicrons to about 30 microm (average size: 2 microm or less) were identified. Compared to well-defined standards, all investigated DU particles were oxidized. About 50% of the DU particles were characterized as UO2, the remaining DU particles present were U3O8 or a mixture of oxidized forms (ca. 2/3 UO2, 1/3 U3O8). Since the particle weathering rate is expected to be higher for U3O8 than for UO2, the presence of respiratory U3O8 and UO2 particles, their corresponding weathering rates and subsequent remobilisation of U from DU particles should be included in the environmental or health impact assessments.     

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.     

Solid state speciation and potential bioavailability of depleted uranium particles from Kosovo and Kuwait

A combination of synchrotron radiation based X-ray microscopic techniques (μ-XRF, μ-XANES, μ-XRD) applied on single depleted uranium (DU) particles and semi-bulk leaching experiments has been employed to link the potential bioavailability of DU particles to site-specific particle characteristics. The oxidation states and crystallographic forms of U in DU particles have been determined for individual particles isolated from selected samples collected at different sites in Kosovo and Kuwait that were contaminated by DU ammunition during the 1999 Balkan conflict and the 1991 Gulf war. Furthermore, small soil or sand samples heavily contaminated with DU particles were subjected to simulated gastrointestinal fluid (0.16 M HCl) extractions. Characteristics of DU particles in Kosovo soils collected in 2000 and in Kuwait soils collected in 2002 varied significantly depending on the release scenario and to some extent on weathering conditions. Oxidized U (+6) was determined in large, fragile and bright yellow DU particles released during fire at a DU ammunition storage facility and crystalline phases such as schoepite (UO₃·2.25H₂O), dehydrated schoepite (UO₃·0.75H₂O) and metaschoepite (UO₃·2.0H₂O) were identified. As expected, these DU particles were rapidly dissolved in 0.16 M HCl (84 ± 3% extracted after 2 h) indicating a high degree of potential mobility and bioavailability. In contrast, the 2 h extraction of samples contaminated with DU particles originating either from corrosion of unspent DU penetrators or from impacted DU ammunition appeared to be much slower (20–30%) as uranium was less oxidized (+4 to +6). Crystalline phases such as UO₂, UC and metallic U or U–Ti alloy were determined in impacted DU particles from Kosovo and Kuwait, while the UO_2,34 phase, only determined in particles from Kosovo, could reflect a more corrosive environment. Although the results are based on a limited number of DU particles, they indicate that the structure and extractability of DU particles released from similar sources (metallic U penetrators) will depend on the release scenarios (fire, impact) and to some extent environmental conditions. However, most of the DU particles (73–96%) in all investigated samples were dissolved in 0.16 M HCl after one week indicating that a majority of the DU material is bioaccessible.     

Plutonium contamination from accidental release or simply fallout: study of soils at Palomares (Spain)

The activity concentration of plutonium in an environmental sample does not usually constitute sufficient information to determine if it is due only to fallout. Alpha and gamma spectrometry are used here conjointly in the study of environmental soil samples to distinguish between samples showing plutonium contamination due to fallout exclusively, and samples contaminated with plutonium from another source. The method was applied to soil samples collected in Palomares (Spain), where an accidental release of aerosols contaminated with plutonium occurred. The two contributions (fallout and accidentally released plutonium) were separated by means of the activity ratios between various radionuclides present in the samples analyzed. The fallout level was estimated from the 239 + 240Pu/137Cs activity ratio. For samples showing contamination due to the accident, the 238Pu/239 + 240Pu and 239Pu/240Pu activity ratios were also calculated to determine the grade of plutonium of this contamination.     

Environmental and health consequences of depleted uranium use in the 1991 Gulf War

Depleted uranium (DU) is a by-product of the 235U radionuclide enrichment processes for nuclear reactors or nuclear weapons. DU in the metallic form has high density and hardness as well as pyrophoric properties, which makes it superior to the classical tungsten armour-piercing munitions. Military use of DU has been recently a subject of considerable concern, not only to radioecologists but also public opinion in terms of possible health hazards arising from its radioactivity and chemical toxicity. In this review, the results of uranium content measurements in different environmental samples performed by authors in Kuwait after Gulf War are presented with discussion concerning possible environmental and health effects for the local population. It was found that uranium concentration in the surface soil samples ranged from 0.3 to 2.5 microg g(-1) with an average value of 1.1 microg g(-1), much lower than world average value of 2.8 microg g(-1). The solid fallout samples showed similar concentrations varied from 0.3 to 1.7 microg g(-1) (average 1.47 microg g(-1)). Only the average concentration of U in solid particulate matter in surface air equal to 0.24 ng g(-1) was higher than the usually observed values of approximately 0.1 ng g(-1) but it was caused by the high dust concentration in the air in that region. Calculated on the basis of these measurements, the exposure to uranium for the Kuwait and southern Iraq population does not differ from the world average estimation. Therefore, the widely spread information in newspapers and Internet (see for example: [CADU NEWS, 2003. http://www.cadu.org.uk/news/index.htm (3-13)]) concerning dramatic health deterioration for Iraqi citizens should not be linked directly with their exposure to DU after the Gulf War.     

Determination of extremely low (236)U/(238)U isotope ratios in environmental samples by sector-field inductively coupled plasma mass spectrometry using high-efficiency sample introduction

A method by inductively coupled plasma mass spectrometry (ICP-MS) was developed which allows the measurement of (236)U at concentration ranges down to 3 x 10(-14)g g(-1) and extremely low (236)U/(238)U isotope ratios in soil samples of 10(-7). By using the high-efficiency solution introduction system APEX in connection with a sector-field ICP-MS a sensitivity of more than 5,000 counts fg(-1) uranium was achieved. The use of an aerosol desolvating unit reduced the formation rate of uranium hydride ions UH(+)/U(+) down to a level of 10(-6). An abundance sensitivity of 3 x 10(-7) was observed for (236)U/(238)U isotope ratio measurements at mass resolution 4000. The detection limit for (236)U and the lowest detectable (236)U/(238)U isotope ratio were improved by more than two orders of magnitude compared with corresponding values by alpha spectrometry. Determination of uranium in soil samples collected in the vicinity of Chernobyl nuclear power plant (NPP) resulted in that the (236)U/(238)U isotope ratio is a much more sensitive and accurate marker for environmental contamination by spent uranium in comparison to the (235)U/(238)U isotope ratio. The ICP-MS technique allowed for the first time detection of irradiated uranium in soil samples even at distances more than 200 km to the north of Chernobyl NPP (Mogilev region). The concentration of (236)U in the upper 0-10 cm soil layers varied from 2 x 10(-9)g g(-1) within radioactive spots close to the Chernobyl NPP to 3 x 10(-13)g g(-1) on a sampling site located by >200 km from Chernobyl.     

Classification of soil samples according to their geographic origin using gamma-ray spectrometry and principal component analysis

A principal component analysis (PCA) was used for classification of soil samples from different locations in Serbia and Montenegro. Based on activities of radionuclides ((226)Ra, (238)U, (235)U, (40)K, (134)Cs, (137)Cs, (232)Th and (7)Be) detected by gamma-ray spectrometry, the classification of soils according to their geographical origin was performed. Application of PCA to our experimental data resulted in satisfactory classification rate (86.0% correctly classified samples). The obtained results indicate that gamma-ray spectrometry in conjunction with PCA is a viable tool for soil classification.     

Significant radioactive contamination of soil around a coal-fired thermal power plant

Soil samples were collected around a coal-fired power plant from 81 different locations. Brown coal, unusually rich in uranium, is burnt in this plant that lies inside the confines of a small industrial town and has been operational since 1943. Activity concentrations of the radionuclides 238U, 226Ra, 232Th, 137Cs and 40K were determined in the samples. Considerably elevated concentrations of 238U and 226Ra have been found in most samples collected within the inhabited area. Concentrations of 235U and 226Ra in soil decreased regularly with increasing depth at many locations, which can be explained by fly-ash fallout. Concentrations of 235U and 226Ra in the top (0-5 cm depth) layer of soil in public areas inside the town are 4.7 times higher, on average, than those in the uncontaminated deeper layers, which means there is about 108 Bq kg(-1) surplus activity concentration above the geological background. A high emanation rate of 222Rn from the contaminated soil layers and significant disequilibrium between 238U and 226Ra activities in some kinds of samples have been found.     

234U and 230Th determination by FIA-ICP-MS and application to uranium-series disequilibrium in marine samples

A 234U and 230Th determination method based on an extraction chromatographic separation on a flow injection system coupled to a quadruple ICP-MS was developed. Two-milliliter UTEVA (Eichrom Co.) cartridges were applied as separation tool and 236U and 229Th as spikes. Loading and washing steps were carried out in 3 M HNO3 solution and 0.05 M ammonium oxalate applied to elute both uranium and thorium. The method was applied initially to the IAEA-327 soil reference sample and NIST SRM 4357 ocean sediment reference material, with the obtained 234U and 230Th concentrations in agreement with the reference levels. Samples from a deep-sea sediment core (2450 m water depth) were analyzed and based on 230Th/234U dating, a mean sedimentation rate of 3.3 cm ky(-1) was calculated. Samples from two sediment layers were also dated by 14C-AMS and the observed ages agree with the 230Th/234U results.     

226Ra/238U disequilibrium in an upland organic soil exhibiting elevated natural radioactivity

This paper presents the results of a study into the anomalous 226Ra/238U disequilibrium (226Ra/238U of 0.5-9) exhibited by an upland organic soil in Co. Donegal, Ireland. Radiochemical speciation of 226Ra, 238U and 225Ra indicates that in this organic soil the high 226Ra/238U ratio is due to loss of 235U relative to 226Ra via oxidation and mobilisation of 238U in the upper layers of the soil and subsequent loss in solution. At the lower, more reducing depths of the soil profile, 238U and 226Ra are essentially in equilibrium. Loss of 238U appears to occur primarily from the easily oxidised organic and iron oxide fractions of the soil, samples exhibiting high 226Ra/238U ratios displaying significantly lower 238U levels in these fractions than samples whose ratio is below the average value for the soil of the valley. Selective enrichment of 226Ra by plants or preferential leaching of 226Ra from the underlying rock is not supported by the results of this study.     

Military use of depleted uranium: assessment of prolonged population exposure

This work is an exposure assessment for a population living in an area contaminated by the use of depleted uranium (DU) weapons. RESRAD 5.91 code was used to evaluate the average effective dose at depths of 1, 10, 20 cm of contaminated soil, in a residential farming scenario. Critical pathways and groups are identified in soil inhalation and ingestion; critical group is identified in children playing with the soil. From the available information on DU released at targeted sites, both critical and average exposure can produce toxicological hazards. The annual dose limit for the population can be exceeded within a few years from DU deposition for soil inhalation. As a result, clean up at targeted sites must be planned on the basis of measured concentration, when available, while special measures must be adopted anyway to reduce unaware exposures.     

The biokinetics of uranium migrating from embedded DU fragments

Military uses of depleted uranium (DU) munitions have resulted in casualties with embedded DU fragments. Assessment of radiological or chemical health risks from these fragments requires a model relating urinary U to the rate of migration of U from the fragments, and its accumulation in systemic tissues. A detailed biokinetic model for U has been published by the International Commission on Radiological Protection (ICRP), but its applicability to U migrating from embedded DU fragments is uncertain. Recently, Pellmar and colleagues (1999) conducted a study at the Armed Forces Radiobiology Research Institute (AFRRI) on the redistribution and toxicology of U in rats with implanted DU pellets, simulating embedded fragments. This paper compares the biokinetic data from that study with the behavior of commonly studied forms of U in rats (e.g., intravenously injected U nitrate). The comparisons indicate that the biokinetics of U migrating from embedded DU is similar to that of commonly studied forms of U with regard to long-term accumulation in kidneys, bone, and liver. The results provide limited support for the application of the ICRP's model to persons with embedded DU fragments. Additional information is needed with regard to the short-term behavior of migrating U and its accumulation in lymph nodes, brain, testicles, and other infrequently studied U repositories.     

Determination of total content and isotopic compositions of plutonium and uranium in environmental samples for safeguards purposes by ICP-QMS

The aim of this work was to determine the concentrations and isotopic compositions of plutonium and uranium in environmental samples for safeguards purposes. An analytical method was developed with a plutonium and uranium separation procedure based on extraction chromatography (using 2 mL TEVA and UTEVA columns) and detection with a quadrupole ICP-MS applying an ultra-sonic nebulizer coupled with a membrane desolvation system. Starting from blank swipes, the background equivalent concentration (BEC) was 8 fg for ²³⁹Pu and 1 ng ²³⁸U. The method was successfully applied to certified reference materials as well as to round robin samples obtained in the framework of the inter-laboratory exercise program, promoted by the Brazilian–Argentine Agency for Accounting and Control of Nuclear Materials (ABACC), together with the US Department of Energy (USDOE). After the introduction of an additional ion-exchange separation step, the methodology was applied to the IAEA-384 sediment reference sample with precise and accurate total plutonium and uranium, ²⁴⁰Pu/²³⁹Pu, ²⁴¹Pu/²³⁹Pu, ²³⁴U/²³⁸U and ²³⁵U/²³⁸U atomic ratio results.