Radionuclide speciation and its relevance in environmental impact assessments

To assess the long-term environmental impact of radioactive contamination of ecosystems, information on source terms including radionuclide speciation, mobility and biological uptake is needed. A major fraction of refractory radionuclides released from nuclear sources such as nuclear weapons tests and reactor accidents is present as radioactive particles, whilst radionuclides are also present as colloids or low molecular mass species in effluents from nuclear installations. Low molecular mass species are more mobile (lower apparent K(d)) and bioavailable (higher apparent BCF) than colloids and particles. Soils and sediments act as sinks for particles and colloids. Due to particle weathering, associated radionuclides can be remobilised over time. Thus, information on particle characteristics such as composition, particle size, crystalline structures and oxidation states influencing weathering rates and subsequent mobilisation is essential. The present article summarises current knowledge on radioactive particles released from different sources, and the relevance of radionuclide speciation for mobility and biological uptake.     

Distribution of natural radionuclides in the production and use of phosphate fertilizers in Brazil

The Brazilian phosphate fertilizer is obtained by wet reaction of igneous phosphate rock with concentrated sulphuric acid, giving as final product, phosphoric acid and dehydrated calcium sulphate (phosphogypsum) as by-products. Phosphoric acid is the starting material for triple superphosphate (TSP), single superphosphate (SSP), monoammonium phosphate (MAP) and diammonium phosphate (DAP). The phosphate rock used as raw material presents in its composition radionuclides of the U and Th natural series. Taking this into account, the main aim of this paper is to evaluate the fluxes of natural radionuclides and radioactive disequilibria involved in the Brazilian industrial process of phosphoric acid production; to determine the content of radioactivity in several commercial fertilizers produced by this industry; to estimate their radiological impact in crop soils and the long term exposure due to their application. Radiological characterization of phosphate rock, phosphogypsum and phosphate fertilizers was performed by alpha and gamma spectrometry. The fertilizer samples, which are derived directly from phosphoric acid, MAP and DAP, presented in their composition low activity concentrations for 226Ra, 228Ra and 210Pb. As for U and Th, the concentrations found in MAP and DAP are more significant, up to 822 and 850Bqkg(-1), respectively. SSP and TSP, which are obtained by mixing phosphoric acid with different amounts of phosphate rock, presented higher concentrations of radionuclides, up to 1158Bqkg(-1) for (238)U, 1167Bqkg(-1) for (234)U, 1169Bqkg(-1) for 230Th, 879Bqkg(-1) for 226Ra, 1255Bqkg(-1) for 210Pb, 521Bqkg(-1) for 232Th, 246Bqkg(-1) for 228Ra and 302Bqkg(-1) for 228Th. Long term exposure due to successive fertilizer applications was evaluated. Internal doses due to the application of phosphate fertilizer for 10, 50 and 100 years were below 1mSvy(-1), showing that the radiological impact of such practice is negligible.     

Speciation of radionuclides - analytical challenges within environmental impact and risk assessments

The mobility, biological uptake and accumulation of radionuclides are essentially dependent on the physico-chemical form of the nuclides. As a major fraction of refractory radionuclides released during historical nuclear events is associated with particles, a key analytical challenge within environmental impact and risk assessments is to characterise radioactive particles with respect to properties influencing particle weathering, remobilisation and the subsequent ecosystem transfer of associated radionuclides. Preanalysis techniques are needed to fractionate, identify and localize individual particles in contaminated samples. To obtain information on particle characteristics such as particle size distributions, structures, elemental and radionuclide particle composition as well as oxidation state of matrix elements, solid-state speciation techniques are needed. Electron microscopy as well as X-ray microscopic techniques utilising synchrotron X-ray radiation have proved most useful in providing such information. The present paper summarises the present status on advanced techniques and presents historical sources that have contributed to radioactive particle contamination.     

Environmental monitoring and radioecology: a necessary synergy

Environmental monitoring primarily aims through sampling or by the use of direct detection equipment to quantify the levels of radioactive substances and ionising radiation resulting from human activities and natural sources in the different compartments of the environment. Its objectives are very practical and include the quantification of the environmental sources of ionising radiation and the verification of compliance with regulatory requirements and permit limits for industrial, research and medical activities, as stated by their specific licence. Radioecology is a multidisciplinary science, which attempts to understand and to quantify the behaviour of radionuclides in the environment and the processes ruling their transport through natural and agricultural ecosystems to various receptors such as plants, animals and humans. A second facet of this science covers the assessment of the radiological dose to and effects on man and its environment from present, past or future, even hypothetical, nuclear activities. Despite their different immediate objectives, environmental monitoring and radioecology are complementary. Many examples illustrate the connections between these two approaches. For instance, transfer parameters generated by radioecological studies are necessary to estimate through models the radiological exposure of population, derive from the contamination level measured in a bio-indicator the quantity of radioactivity released from a nuclear installation, or identify potentially important pathways to be monitored. On the other hand, monitoring data will confirm important pathways suggested by radioecological modelling and provide site-specific data for the estimation of model parameters or actual data sets for the validation of transfer models.     

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.     

Radioactive contamination of wood and its products

This paper presents research on radioactive contamination of the three most common kinds of wood in Croatia--beech, oak and fir as well as acorn. Gamma-spectrometric measurements carried out on the samples of bark and wood of beech, oak, fir and acorn have shown radioactivity contents ranging from 1.6 +/- 0.1 to 37.3 +/- 0.5 Bq/kg from deposited 137Cs, whose concentrations in the soil of Croatia have increased after the Chernobyl accident. Measurements have also shown the radioactivity originating from 40K and 214Bi, which are part of the natural composition of the soil. The distribution of the radionuclides in wood has been discussed, as well as the impact of radioactive contamination of wood by the artificial radionuclide 137Cs upon the forest ecosystem. According to the corresponding model, it has been calculated that a 10 h daily stay in a typical family house increases the annual radiation dose of the population, due to the deposited 137Cs in the structure or furniture, by 343 microSv.     

Aerial measurements of artificial radionuclides in Germany in case of a nuclear accident

Gamma-ray spectrometric systems carried by helicopters prove to be indispensable for the surveillance of environmental radioactivity. The aerial measurements are an important tool for rapid and large-scale nuclide specific determination of soil contamination after an accidental release of radionuclides from a nuclear facility. Furthermore this technique is also applied for the determination of anomalies of elevated radioactivity of natural radionuclides, the detection of lost radioactive sources and geological mapping. For the measurements the helicopters are equipped with a NaI(Tl)-detector array and a high purity germanium-semiconductor (HPGe) detector. Especially with the HPGe-detector it is possible to clearly identify individual radionuclides. To improve and to guarantee the quality of this method several exercises with different fields of interest have been carried out during the last years. Thereby the main focus is on the improvement of the instrumentation, data handling and data analysis. The results of the airborne radionuclide measurements from the Black Forest which was performed in co-operation with the Swiss National Emergency Operation Centre, are presented here. During this exercise the gamma dose rate, soil contamination due to 137Cs and the specific activities of natural radionuclides in soil were determined.     

Radioactive impact of Fukushima accident on the Iberian Peninsula: evolution and plume previous pathway

High activity concentrations of several man-made radionuclides (such as (131)I, (132)I, (132)Te, (134)Cs and (137)Cs) have been detected along the Iberian Peninsula from March 28th to April 7th 2011. The analysis of back-trajectories of air masses allowed us to demonstrate that the levels of manmade radionuclide activity concentrations in the southwest of the Iberian Peninsula come from the accident produced in the nuclear power plant of Fukushima. The pathway followed by the radioactive plume from Fukushima into Huelva (southwest of the Iberian Peninsula) was deduced through back-trajectories analysis, and this fact was also verified by the activity concentrations measured of those radionuclides reported in places crossed by this radioactive cloud. In fact, activity concentrations reported by E.P.A., and by IAEA, in several places of Japan, Pacific Ocean and United States of America are according to the expected ones from the air mass trajectory arriving at Huelva province.     

Status report on standard-setting work in the area of environmental radioactivity measurement

Environmental assessment studies are regularly commissioned to study the impact of radioactive substances on the environment and the public, in response to concern about the presence of such substances. The credibility of such studies relies on the quality and reliability of radionuclide analysis as well as the sample representativity of the radiological situation. The recent expansion from national stakeholders to those involving other states requires that activity measured in effluents or environmental samples in a country are reliable and reproducible so as to be accepted by all states potentially concerned by regional contamination. The standard-setting approach, based on consensus, seemed to lend itself to a settlement of technical aspects of potential dispute. This document describes standardization organizations, French and international, the standards published, as well as standardization work under way on the measurement of radionuclides found in environmental matrices.     

Results of the European Commission Marina II study: part II--effects of discharges of naturally occurring radioactive material

Enhanced levels of naturally occurring radioactive materials (NORM) are produced through various industrial operations and may lead to discharges to the marine environment. A recent study, called MARINA II, carried out for the European Commission considered discharges of radionuclides from the NORM industries to north European marine waters and their consequences. There are two main sources that were considered in the study. The use of phosphogypsum during the production of phosphoric acid by the fertiliser industry and the pumping of oil and gas from the continental shelf in the North Sea which produces large quantities of water contaminated with enhanced levels of naturally occurring radionuclides. Discharges of alpha emitting radionuclides from these two industries have contributed significantly to the total input of alpha emitters to north European waters over the period 1981-2000 (data were not available prior to 1981). Discharges due to the use of phosphogypsum have declined since the early 1990s and are now very low. Discharges from the oil and gas industries stabilised in the second half of the 1990s and are now the major contributor to alpha discharges to the region. As most European countries do not report discharges of radioactivity with the water produced during extraction, there is considerable uncertainty in the discharges used in the study. The impact of the discharges has been estimated both in terms of the effect on non-human biota and the radiological impact for people. In the 1980s the radiation dose rates to marine biota in the region around a phosphate plant on the north-west coast of England were as high due to the discharges from the phosphate plant as those near to the Sellafield reprocessing plant due to its discharges. In recent years the additional dose to marine biota in this region due to the past NORM discharges is of the same order of magnitude as the natural background. The collective dose rate was estimated to determine the radiological impact on people. The peak collective dose rate from the NORM industries occurred in 1984 and was just over 600 manSv y(-1). The collective dose rate fell with time as discharges from the phosphate industry reduced and was estimated as under 200 manSv y(-1) in 2000.     

Evidence of the radioactive fallout in the center of Asia (Russia) following the Fukushima Nuclear Accident

It was recently reported that radioactive fallout due to the Fukushima Nuclear Accident was detected in environmental samples collected in the USA and Greece, which are very far away from Japan. In April-May 2011, fallout radionuclides (¹³⁴Cs, ¹³⁷Cs, ¹³¹I) released in the Fukushima Nuclear Accident were detected in environmental samples at the city of Krasnoyarsk (Russia), situated in the center of Asia. Similar maximum levels of ¹³¹I and ¹³⁷Cs/¹³⁴Cs and ¹³¹I/¹³⁷Cs ratios in water samples collected in Russia and Greece suggest the high-velocity movement of the radioactive contamination from the Fukushima Nuclear Accident and the global effects of this accident, similar to those caused by the Chernobyl accident.     

Long-term investigation of anthropogenic and naturally occurring radionuclides at reference sites in western Sweden

In case of an accidental release of radioactive substances into the environment, it is important to quickly and reliably estimate the radiation dose received by people in the affected area, and to determine the extent of the contamination. Measurements of the extent of the release and the subsequent contamination can be facilitated if there are predetermined reference sampling sites with known background radiation and inventory of radionuclides. Since 1996, 34 reference sites for soil sampling, field gamma, and intensimeter measurements have been established in western Sweden. Time series data for dose rates and radioisotope inventory have been collected at these sites, allowing for the investigation of changes in these parameters over time. The mass activity densities for the uranium and thorium series elements varied approximately between 10 and 50 Bq/kg and between 10 and 40 Bq/kg, respectively. The mass activity density of ⁴⁰K was approximately in the range 300–800 Bq/kg. The radiation exposure due to ¹³⁷Cs was rather small in this area. The dose rates calculated from in situ measurement data showed that the contribution to the total dose rate was almost entirely due to naturally occurring radionuclides. The measured dose rate was about twice as high as the calculated rate, even after subtracting the contribution from cosmic radiation. This may be explained by the fact that intensimeters generally are calibrated to measure the quantity ambient dose equivalent, which should not underestimate the effective dose.     

Transport and distribution of artificial gamma-emitting radionuclides in the River Yenisei and its sediment

Discharges from the Krasnoyarsk Mining and Chemical Industrial Complex (KMCIC) near Krasnoyarsk resulted in radioactive contamination of sediments of the River Yenisei. Between 1999 and 2006, 16 sediment cores were collected at different positions 15-1500 km downstream from the discharge point. The concentration of artificial gamma-emitting radionuclides (¹³⁷Cs, ⁶⁰Co, ¹⁵²Eu, and ²⁴¹Am) was determined with the objective to analyze the migration processes leading to the transport of these radionuclides along the river and to their vertical distribution within the sediment. In cores taken in the vicinity of the reactors, the average activity concentration of ¹³⁷Cs, ¹⁵²Eu, and ⁶⁰Co was about 1000 Bq kg⁻¹, and the activity concentration of ²⁴¹Am was about 20 Bq kg⁻¹. Contamination levels of artificial radionuclides were decreasing with increasing distance downstream the KMCIC: The fastest decrease of average activity by a factor of 10 over a distance of 300 km was observed for ²⁴¹Am, whereas for ¹³⁷Cs this decrease occurred over a distance of 1100 km. Sequential extraction experiments revealed that in all depths and at all distances the studied radionuclides were tightly bound to the sediment.To investigate the mechanisms of transport of the ¹³⁷Cs and ⁶⁰Co contamination, mathematical models have been used to describe the contamination in the river water and within the sediments.     

Assessing field-scale migration of radionuclides at the Nevada Test Site: "mobile" species

Many long-lived radionuclides are present in groundwater at the Nevada Test Site (NTS) as a result of 828 underground nuclear weapons tests conducted between 1951 and 1992. In conjunction with a comprehensive geochemical review of radionuclides ((3)H, (14)C, (36)Cl, (99)Tc and (129)I) that are presumably mobile in the subsurface, we synthesized a body of radionuclide activity data measured from groundwater samples collected at 18 monitoring wells, to qualitatively assess their migration at the NTS over distances of hundreds of meters and over timescales of decades. Tritium and (36)Cl showed little evidence of retardation, while the transport of (14)C may have been retarded by its isotopic exchange with carbonate minerals in the aquifer. Observed local reducing conditions (either natural or test-induced) will impact the mobility of certain redox-sensitive radionuclides (especially (99)Tc) that were otherwise soluble and readily transported under oxidizing conditions. Conversely, strongly oxidizing conditions may impact the mobility of (129)I which is mobile under reducing conditions. The effect of iodine speciation on its transport deserves further attention. Indication of delayed transport of some "mobile" radionuclides (especially (99)Tc) in the groundwater at the NTS suggested the importance of redox conditions of the natural system in controlling the fate and transport of radionuclides, which has implications in the enhanced performance of the potential Yucca Mountain repository, located adjacent to the NTS, to store high-level nuclear wastes as well as management of radionuclide contamination in legacy nuclear operations facilities.     

Aspects of the uptake of radionuclides by sheep grazing on an estuarine saltmarsh. 1. The influence of grazing behaviour and environmental variability on daily intake

Sea water contaminated with diluted radioactive effluent originating from the Sellafield reprocessing plant inundates saltmarshes in the Esk estuary in west Cumbria (UK). Much of the radioactivity on the saltmarsh vegetation was found to be associated with a surface deposit of silt, brought onto the area during tidal inundation. Large temporal variations in the radionuclide concentrations of the vegetation were found, these being due probably to seasonal fluctuation in the extent of silt deposition.The grazing habits of sheep were studied on one of these saltmarshes and the consequent ingestion of radionuclides by the sheep was estimated. The sheep ingested different quantities of radionuclides according to time of year as a result of a combination of two factors; the considerable temporal variation in the concentration of radionuclides on the saltmarsh vegetation and the seasonal grazing behaviour of the sheep.     

A comparison of the soil migration and plant uptake of radioactive chlorine and iodine from contaminated groundwater

A 6-month soil column experiment was conducted to compare the upward migration and plant uptake of radiochlorine and radioiodine from shallow, near-surface contaminated water tables. Both fixed and fluctuating water tables were studied. After 6 months, (36)Cl activity concentrations were relatively uniform throughout the soil profile apart from an accumulation at the soil surface, which was especially marked under a fluctuating water table scenario. In contrast, (125)I (a surrogate for (129)I) tended to accumulate at the boundary between the anoxic conditions at the base of the column and the oxic conditions above, due to its redox-dependent sorption behaviour. The uptake of (36)Cl by perennial ryegrass was much greater than that of (125)I due to its greater migration into the rooting zone and its ready availability in soil solution. In the context of radioactive waste disposal, where these radionuclides may potentially be released into groundwater, (36)Cl would be expected to present a greater potential for contamination of the biosphere than (129)I.     

Assessment of the radiological impacts of historical coal mining operations on the environment of Ny-Alesund, Svalbard

Mineral extraction activities, such as those conducted by oil, gas and coal industries, are widespread throughout the Arctic region. Waste products of these activities can result in significant contributions to the radioactive burden of the surrounding environment due to increased concentrations of naturally occurring radioactive materials (NORM) to levels that would not normally be found in the environment. Coal mining operations commenced in the early 1900s on Svalbard and have been conducted at a variety of locations on the archipelago since then. Coal contains radionuclides of the uranium and thorium series as well as 40K. Extraction and processing of coal can result in releases of these radionuclides to the broader environment with subsequent impact on the human and non-human inhabitants of the area. This paper presents the results of a study on environmental radioactivity resulting from historical coal mining operations conducted at Ny-Alesund, Spitsbergen, in the Svalbard archipelago. Activity concentrations of radionuclides found in materials associated with these operations are presented as well as the results of a spatial dosimetric survey conducted over an area affected by coal mining.     

Coupled anthropogenic anomalies of radionuclides and major elements in estuarine sediments

Concentrations of fertilizer industry-derived P (up to 3.4%), Ca (up to 6.1%), (226)Ra (up to 744 Bq kg(-1)) and (210)Pb (up to 1317 Bq kg(-1)) at least one order of magnitude above natural levels were recorded in a sediment core from Morr?o River estuary (SE Brazil). Unsupported (210)Pb (= total (210)Pb-(226)Ra) activities unexplained by atmospheric fallout and deviations from the radionuclides secular equilibrium also indicated strong anomalies. Anomalous constituents were positively correlated with each other and negatively correlated with clay mineral-bearing elements. These negative correlations were explained by a depletion of natural sediment constituents due to a dilution caused by elevated inputs of steel industry-derived elements (mainly by Fe levels up to 24%). Absolute data and normalizations by a proxy for clays (Al) and anthropogenic Fe evidenced variabilities in the quality of coastal and land-derived sediment inputs, mainly due to changes in the relative contributions from industrial sources.     

Tidal variations in dissolved and particulate phase radionuclide activities in the Esk estuary,England, and their distribution coefficients and particulate activity fractions

Measurements have been made of the radionuclide activities, particularly for plutonium isotopes, of the particulate and dissolved fractions of the tidal waters of the Esk Estuary. A wide range of K_d values indicates the lack of equilibrium conditions in this dynamically changing environment. The particulate activity contributes a major part of the activity of the suspension, with reworked estuarine sediment providing an important component of this. The estuarine circulation system results in the dispersion of particulate radionuclides into the low salinity upper reaches of the estuary, where plutonium isotopes are apparently mobilised, enriching the dissolved fraction activity.     

Technologically enhanced 210Pb and 210Po in iron and steel industry

Iron and steel manufacture has been ranked as the largest industrial source of environmental contamination in the USA; the wastes generated in their production processes contain heavy elements that can be a source of contamination, and natural radionuclides that can produce an occupational and/or public radiological impact. In this work the potential occupational effective dose rate (μSv/y) due to inhalation in four integrated steel-making factories from Egypt has been evaluated, by assuming a well defined scenario and with basis in the ²¹⁰Pb and ²¹⁰Po activity concentrations determined in ore and wastes collected in the aforementioned factories. Activity concentrations, in Bq/kg, of ²¹⁰Pb and ²¹⁰Po, and leachable Pb and Fe were measured using gamma-ray spectrometry based on HPGe detector, alpha particle spectrometry based on PIPS detector, and inductively coupled plasma-mass spectrometry (ICP-MS). Levels of ²¹⁰Pb and ²¹⁰Po in the range of <DL-4238 and 1-5660 Bq/kg, respectively, were found. According to the assumed scenarios, the occupational exposures by inhalation are much lower than the recommended annual effective dose limit, although the environmental impact due to waste storage and/or use should be considered based on case by case evaluation.