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.     

Health risk assessment for uranium in Korean groundwater

We analyzed the radiological and chemical risks of uranium in groundwater. The total sample number over 4 years was 498. There were several use patterns of groundwater in Korea, but we considered the risk only for drinking water. The geometric mean of uranium concentration in 10 areas in Korea was 0.17 microg x l(-1). The excess cancer risks were in the 10(-7) level in the radiological risk aspect and the hazard quotient was 0.005 in the chemical risk aspect. Therefore, we could conclude that an adverse health risk is unlikely to be posed due to exposure to uranium. However, the concentration of uranium must be monitored periodically and adequate action taken in the few and small areas that contain high uranium levels in groundwater.     

Principles and issues in radiological ecological risk assessment

This paper provides a bridge between the fields of ecological risk assessment (ERA) and radioecology by presenting key biota dose assessment issues identified in the US Department of Energy's Graded Approach for Evaluating Radiation Doses to Aquatic and Terrestrial Biota in a manner consistent with the US Environmental Protection Agency's framework for ERA. Current radiological ERA methods and data are intended for use in protecting natural populations of biota, rather than individual members of a population. Potentially susceptible receptors include vertebrates and terrestrial plants. One must ensure that all media, radionuclides (including short-lived radioactive decay products), types of radiations (i.e., alpha particles, electrons, and photons), and pathways (i.e., internal and external contamination) are combined in each exposure scenario. The relative biological effectiveness of alpha particles with respect to deterministic effects must also be considered. Expected safe levels of exposure are available for the protection of natural populations of aquatic biota (10 mGy d(-1)) and terrestrial plants (10 mGy d(-1)) and animals (1 mGy d(-1)) and are appropriate for use in all radiological ERA tiers, provided that appropriate exposure assumptions are used. Caution must be exercised (and a thorough justification provided) if more restrictive limits are selected, to ensure that the supporting data are of high quality, reproducible, and clearly relevant to the protection of natural populations.     

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.     

Regional risk assessment for contaminated sites part 2: ranking of potentially contaminated sites

Environmental risks are traditionally assessed and presented in non spatial ways although the heterogeneity of the contaminants spatial distributions, the spatial positions and relations between receptors and stressors, as well as the spatial distribution of the variables involved in the risk assessment, strongly influence exposure estimations and hence risks. Taking into account spatial variability is increasingly being recognized as a further and essential step in sound exposure and risk assessment. To address this issue an innovative methodology which integrates spatial analysis and a relative risk approach was developed. The purpose of this methodology is to prioritize sites at regional scale where a preliminary site investigation may be required. The methodology aimed at supporting the inventory of contaminated sites was implemented within the spatial decision support sYstem for Regional rIsk Assessment of DEgraded land, SYRIADE, and was applied to the case-study of the Upper Silesia region (Poland). The developed methodology and tool are both flexible and easy to adapt to different regional contexts, allowing the user to introduce the regional relevant parameters identified on the basis of user expertise and regional data availability. Moreover, the used GIS functionalities, integrated with mathematical approaches, allow to take into consideration, all at once, the multiplicity of sources and impacted receptors within the region of concern, to assess the risks posed by all contaminated sites in the region and, finally, to provide a risk-based ranking of the potentially contaminated sites.     

Regional risk assessment for contaminated sites Part 2: Ranking of potentially contaminated sites

Environmental risks are traditionally assessed and presented in non spatial ways although the heterogeneity of the contaminants spatial distributions, the spatial positions and relations between receptors and stressors, as well as the spatial distribution of the variables involved in the risk assessment, strongly influence exposure estimations and hence risks. Taking into account spatial variability is increasingly being recognized as a further and essential step in sound exposure and risk assessment. To address this issue an innovative methodology which integrates spatial analysis and a relative risk approach was developed. The purpose of this methodology is to prioritize sites at regional scale where a preliminary site investigation may be required. The methodology aimed at supporting the inventory of contaminated sites was implemented within the spatial decision support sYstem for Regional rIsk Assessment of DEgraded land, SYRIADE, and was applied to the case-study of the Upper Silesia region (Poland).The developed methodology and tool are both flexible and easy to adapt to different regional contexts, allowing the user to introduce the regional relevant parameters identified on the basis of user expertise and regional data availability. Moreover, the used GIS functionalities, integrated with mathematical approaches, allow to take into consideration, all at once, the multiplicity of sources and impacted receptors within the region of concern, to assess the risks posed by all contaminated sites in the region and, finally, to provide a risk-based ranking of the potentially contaminated sites.     

Regional risk assessment for contaminated sites part 1: vulnerability assessment by multicriteria decision analysis

As highlighted in the EU Soil Communication, local contamination is one of the main soil threats and it is often related to present and past industrial activities which left a legacy of a high number of contaminated sites in Europe. These contaminated sites can be harmful to many different receptors according to their sensitivity/susceptibility to contamination, and specific vulnerability evaluations are needed in order to manage this widely spread environmental issue. In this paper a novel comprehensive vulnerability assessment framework to assess regional receptor susceptibility to contaminated site is presented. The developed methodology, which combines multi criteria decision analysis (MCDA) techniques and spatial analysis, can be applied to different receptors recognized as relevant for regional assessment. In order to characterize each receptor, picked parameters significant for the estimation of the vulnerability to contaminated sites have been selected, normalized and aggregated by means of multi criteria decision analysis (MCDA) techniques. The developed MCDA methodology, based on the Choquet integral, allows to include expert judgments for the elicitation of synergic and conflicting effects between involved criteria and is applied to all the geographical objects representing the identified receptors. To test the potential of the vulnerability methodology, it has been applied to a specific case study area in the upper Silesia region of Poland where it proved to be reliable and consistent with the environmental experts' expected results. The vulnerability assessment results indicate that groundwater is the most vulnerable receptor characterized by a wide area with vulnerability scores belonging to the highest vulnerability class. As far as the other receptors are concerned, human health and surface water are characterized by quite homogeneous vulnerability scores falling in the medium-high vulnerability classes, while protected areas resulted to be the less vulnerable receptor with only one protected area falling in the medium vulnerability class. The vulnerability assessment results will support the regional risk assessment for the ranking of potentially contaminated sites at regional scale.     

Regional risk assessment for contaminated sites Part 3: Spatial decision support system

Large scale (e.g. regional or national) assessments of contaminated sites may be very costly in terms of investigation and methodological (i.e. risk assessment procedures) requirements and may produce a quantity of information that usually discourages examination by decision-makers. Moreover, most of the existing tools effectively support local environmental risk assessment and management, but lack the capabilities of larger scale analysis, not mentioning the absence of the relevant component of socio-economic prioritization. To respond to the concerns and the management needs of experts and decision makers, the Spatial decision support sYstem for Regional rIsk Assessment of Degraded land (SYRIADE DSS) was developed and is presented according to its three modules: Regional Risk Assessment, Socio-economic Assessment and Integrated Assessment, respectively. The system allows to rank potentially contaminated sites for priority of investigation, when no information on characterization and risk by site specific methodologies is available. This GIS-based system embeds an innovative spatial and relative risk assessment procedure, and proposes the integrated analysis of different data (environmental and socio-economic) for the concerned sites, eliciting when necessary experts' knowledge and stakeholders' values (through Multi Criteria Decision Analysis, MCDA, methodologies). The application to a Polish case-study shows the performance and the flexibility of the system in investigating and mapping (potentially) contaminated sites at the regional scale.     

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.     

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).     

Dynamic model for the assessment of radiological exposure to marine biota

A generic approach has been developed to simulate dynamically the uptake and turnover of radionuclides by marine biota. The approach incorporates a three-compartment biokinetic model based on first order linear kinetics, with interchange rates between the organism and its surrounding environment. Model rate constants are deduced as a function of known parameters: biological half-lives of elimination, concentration factors and a sample point of the retention curve, allowing for the representation of multi-component release. The new methodology has been tested and validated in respect of non-dynamic assessment models developed for regulatory purposes. The approach has also been successfully tested against research dynamic models developed to represent the uptake of technetium and radioiodine by lobsters and winkles. Assessments conducted on two realistic test scenarios demonstrated the importance of simulating time-dependency for ecosystems in which environmental levels of radionuclides are not in equilibrium.     

Endocrine disrupting pesticides: implications for risk assessment

Endocrine disrupting (ED) chemicals are compounds that alter the normal functioning of the endocrine system, potentially causing disease or deformity in organisms and their offspring. Pesticides are used widely to kill unwanted organisms in crops, public areas, homes and gardens and medicinally to kill parasites. Many are proven or suspected to be EDs. Ancient physiological similarities between different vertebrate groups suggest that disorders observed in wildlife may indicate risks to humans. This makes accurate risk assessment and effective legislation difficult. In this paper, the hazardous properties of pesticides which are known to have ED properties are reviewed in order to assess the implications for risk assessment. As well as data on sources of exposure in the United Kingdom (UK) an assessment of the evidence on the health effects of ED pesticides is also included. In total, 127 have been identified from the literature and their effects and modes of action are listed in this paper. Using the UK as a case study, the types and quantities of pesticides used, and their methods of application are assessed, along with their potential pathways to humans. In the UK reliable data are available only for agricultural use, so non-agricultural routes of pesticide exposure have been poorly quantified. The exposure of people resident in or visiting rural areas could also have been grossly under-estimated. Material links between ED pesticide use and specific illnesses or deformities are complicated by the multifactorial nature of disease, which can be affected by factors such as diet. Despite these difficulties, a large body of evidence has accumulated linking specific conditions to ED pesticides in wildlife and humans. A more precautionary approach to the use of ED pesticides, especially for non-essential purposes is proposed.     

Radioecology in the vicinity of prospected uranium mining sites in a subarctic environment

A radioecological investigation has been carried out in two uranium-rich areas in northern Sweden. Aquatic, terrestrial and atmospheric samples have been analysed, mainly for radionuclides in the uranium series. In one of the areas, about ten times higher concentrations of uranium, thorium and radium were found in lichen close to the mineralization, due to aerial dispersion. In the aquatic system, no signs of enhanced levels were observed. For the short-lived radon daughters in air, there was no correlation between concentrations and distance from mineralization, as a result of the high natural background.     

Radioactivity in the environment around past radium and uranium mining sites of Portugal

Measurements of ambient radiation doses and determination of radionuclide concentrations in mining waste and soils were performed in 60 areas of former radium and uranium mining. In several places, mining waste and low-grade uranium ore left on the surface contain radioactivity above regional background. Most of the former mining sites present no enhanced radionuclide concentrations. However, in the mining facilities where the radioactive ore was chemically extracted, mill tailings contain materials with elevated levels of radioactivity, up to 200 times the levels in unaffected soils of the region. Mud from neutralization ponds used to treat acid mine waters contains also elevated radionuclide concentrations. Furthermore, depending on the type of waste, the radioelement composition varies. Environmental rehabilitation measures shall take these differences into account in order to prevent in the long term the radioactive contamination of agriculture soils and water resources, and to ensure adequate radiological protection to the public and to the environment.     

Probabilistic risk assessment for long-range atmospheric transport of radionuclides

A simplified means of probabilistic risk assessment (PRA) for long-range atmospheric transport based on a K-diffusion model is presented. In a case study, model parameters are estimated by comparing with the results of long-range atmospheric dispersion model calculations using one-year numerical weather prediction model data. It is found that the estimated ensemble mean provides a reasonable first approximation to the total dry and wet deposition from the one-year continuous release.     

Frameworks and tools for risk assessment of manufactured nanomaterials

Commercialization of nanotechnologies entails a regulatory requirement for understanding their environmental, health and safety (EHS) risks. Today we face challenges to assess these risks, which emerge from uncertainties around the interactions of manufactured nanomaterials (MNs) with humans and the environment. In order to reduce these uncertainties, it is necessary to generate sound scientific data on hazard and exposure by means of relevant frameworks and tools. The development of such approaches to facilitate the risk assessment (RA) of MNs has become a dynamic area of research. The aim of this paper was to review and critically analyse these approaches against a set of relevant criteria. The analysis concluded that none of the reviewed frameworks were able to fulfill all evaluation criteria. Many of the existing modelling tools are designed to provide screening-level assessments rather than to support regulatory RA and risk management. Nevertheless, there is a tendency towards developing more quantitative, higher-tier models, capable of incorporating uncertainty into their analyses. There is also a trend towards developing validated experimental protocols for material identification and hazard testing, reproducible across laboratories. These tools could enable a shift from a costly case-by-case RA of MNs towards a targeted, flexible and efficient process, based on grouping and read-across strategies and compliant with the 3R (Replacement, Reduction, Refinement) principles. In order to facilitate this process, it is important to transform the current efforts on developing databases and computational models into creating an integrated data and tools infrastructure to support the risk assessment and management of MNs.     

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.     

Towards a non-animal risk assessment for anti-androgenic effects in humans

Toxicology testing is undergoing a transformation from a system based on high-dose studies in laboratory animals to one founded primarily on in vitro methods that evaluate changes in normal cellular signalling pathways using human-relevant cells or tissues. We review the tools and approaches that could be used to develop a non-animal safety assessment for anti-androgenic effects in humans, with a focus on the molecular initiating events (MIEs) that human disorders indicate critical for normal functioning of the hypothalamus–pituitary–testicular (HPT) axis. In vitro test systems exist which can be used to characterize the effects of test chemicals on some MIEs such as androgen receptor antagonism, inhibition of steroidogenic enzymes or 5α-reductase inhibition. When used alongside information describing the pharmacokinetics of a specific chemical exposure, these could be used to inform a pathways-based safety assessment. However, some parts of the HPT axis such as events occurring in the hypothalamus or pituitary are not well represented by accepted in vitro methods. In vitro tools to characterize perturbations in these events need to be developed before a fully integrated model of the HPT axis can be described. Knowledge gaps also exist which prevent us from using in vitro data to predict the type and severity of in vivo effect(s) that could arise from a given level of in vitro anti-androgenic activity. This means that more work is needed to reliably link an MIE with an adverse outcome. However, especially for chemicals with low anti-androgenic activity, human exposure data can be used to put in vitro mode of action data into context for risk-based safety decision-making.     

Environmental risk assessment of metals: tools for incorporating bioavailability

In this paper, some of the main processes and parameters which affect metal bioavailability and toxicity in the aquatic environment and its implications for metal risk assessment procedures will be discussed. It has become clear that, besides chemical processes (speciation, complexation), attention should also be given to physiological aspects for predicting metal toxicity. The development of biotic ligand models (BLMs), which combine speciation models with more biologically oriented models (e.g. GSIM), has offered an answer to this need. The various BLMs which have been developed and/or refined for a number of metals (e.g. Cu, Ag, Zn) and species (algae, crustaceans, fish) are discussed here. Finally, the potential of the BLM approach is illustrated through a theoretical exercise in which chronic zinc toxicity to Daphnia magna is predicted in three regions, taking the physico-chemical characteristics of these areas into account.