Distribution and mobilization of U, Th and 226Ra in the plant-soil compartments of a mineralized uranium area in south-west Spain

The activity concentrations of natural uranium isotopes (238U and 234U), thorium isotopes (232Th, 230Th and 225Th) and 226Ra were studied in soil and vegetation samples from a disused uranium mine located in the Extremadura region in the south-west of Spain. The results allowed us to characterize radiologically the area close to the installation and one affected zone was clearly manifest as being dependent on the direction of the surface water flow from the mine. The activity concentration mean values (Bq/kg) in this zone were: 10,924, 10,900, 10,075 and 5,289 for 238U, 234U, 230Th and 226Ra, respectively, in soil samples and 1,050, 1,060, 768 and 1,141 for the same radionuclides in plant samples. In an unaffected zone, the activity concentration mean values (Bq/kg) were: 184, 190, 234 and 7251 for 235U, 234U, 230Th and 226Ra, respectively, in soil samples and 28. 29, 31 and 80 in plant samples. The activity concentrations obtained for 232Th and 228Th showed that the influence of the mine was only important for the uranium series radionuclides. The relative radionuclide mobilities were determined from the activity ratios. Correlations between radionuclide activity concentrations and stable element concentrations in the soil samples helped to understand the possible distribution paths for the natural radionuclides.     

Radiological impact from atmospheric releases of 238U and 226Ra from phosphate rock processing plants

Phosphate rocks are used extensively, mainly as a source of phosphorus for fertilizers and secondarily for phosphoric acid and other speciality chemicals. Phosphates are typically enriched in uranium and are thus one of the sources of technologically enhanced natural radiation (TENR) which increases exposure to man from natural radionuclides. Emissions from phosphate rock processing plants in gaseous and particulate form contain radionuclides, such as 238U and 226Ra, which are discharged into the environment causing radiation exposures to the population. About 10 MBq each of 238U and 226Ra are discharged into the environment each year from SICNG, a phosphate rock processing plant in Thessaloniki area, Northern Greece. The collective dose commitment to lung tissue resulting from atmospheric releases was estimated to be approximately 2 x 10(-9) person Gy t-1 for 238U and approximately 0.1 x 10(-9) person Gy t-1 for 226Ra, i.e. about 2 times higher than that estimated in the UNSCEAR reports issued in 1982, 1988, and 1993.     

Aerial measurements on uranium ore mining, milling and processing areas in Germany

The paper describes aerial measurements at several sites containing residues from uranium mines, waste rock dumps and tailings ponds of the Wismut company in Saxony and Thuringia. For the measurements, a computerized gamma-ray spectrometer equipped with a HPGe-detector and a NaI(Tl)-detector array with a volume of 121 was used. Radioactive anomalies from natural radionuclides have been detected and mapped. The activity concentrations of 226Ra, 228Th and 40K in areas with elevated radioactivity from natural radionuclides were determined from aerial measurements. Ground-based measurements--as far as available--confirmed these results. The mean 226Ra activity concentrations in the different waste rock dumps were found to be in the range 370 to 1600 Bq kg-1. The highest mean 226Ra activity concentrations were measured for the tailings ponds with values up to 1300 Bq kg-1. For 40K and 208Tl, activity concentrations of 860 and 40 Bq kg-1, respectively, were obtained as averages of all measurements. These values are commonly found in the environment. In general, there is reasonable agreement between the results measured with different detectors and measuring methods.     

Fractionation of natural radionuclides in soils from a uranium mineralized area in the south-west of Spain

A new version of a classical method was applied to study the distribution of natural radionuclides (238U, 230Th, and 226Ra) in the soil fractions obtained by a sequential extraction procedure. The potential significance of the fractions obtained with this method was tested on two very similar soils but with very different contents of the three radionuclides, collected in the proximity of a disused uranium mine located in the Extremadura region in the south-west of Spain. The results confirmed that, if only non-residual fractions are considered, the sequential method applied shows a characteristic speciation pattern of these natural radionuclides in this soil matrix, i.e., the distribution of each of the three radionuclides was very similar for the two soil samples.     

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.     

Intake of uranium and radium-226 due to food crops consumption in the phosphate region of Pernambuco--Brazil

The phosphate region located in the Northeast of Brazil covers an area of approximately 150 km long with an average width of 4 km, along the coast of the states of Pernambuco and Paraíba. The inhabitants of this area are exposed to natural radioactivity levels higher than the background values recorded in the literature, mainly due to the presence of uranium and its decay products in the phosphatic sediments. The main aim of this study was to determine the activity concentration of uranium and (226)Ra in foodstuffs cultivated in this area, where the phosphate mineral has been extracted. The activity concentrations found for uranium and (226)Ra in the foodstuffs analyzed varied from 13 to 186 mBq kg(-1) (wet weight), with a mean value of 46 mBq kg(-1) and from 43 to 2209 mBq kg(-1) (wet weight), with a mean value of 358 mBq kg(-1), respectively. The annual intake of these radionuclides, for rural residents, was 7.45 Bq for uranium and 69.3 Bq for (226)Ra.     

Radiological impacts of natural radioactivity in Abu-Tartor phosphate deposits, Egypt.

Phosphate and environmental samples were collected from Abu Tartor phosphate mine and the surrounding region. The activity concentration of 226Ra (238U) series, 232Th series and 40K were measured using a gamma-ray spectrometer. The activities of uranium isotopes (238U, 235U and 234U) and 210Pb were measured using an alpha spectrometer and a low-background proportional gas counting system, respectively, after radiochemical separation. The results are discussed and compared with the levels in phosphate rocks from different countries. It seems that the Abu Tartor phosphate deposit has the lowest radioactivity level of exploited phosphate of sedimentary origin. 226Ra/238U, 210Pb/226Ra, 234U/238U and 226Ra/228Ra activity ratios were calculated and are discussed. The radioactivity levels in the surrounding region and the calculated exposure dose (nGy/h) will be considered as a pre-operational baseline to estimate the possible radiological impacts due to mining, processing and future phosphate industrial activities. To minimize these impacts, the processing wastes should be recycled to the greatest possible extent.     

Radioecological characterization of a uranium mining site located in a semi-arid region in Brazil

The work presents the radioecological characterization of the new Brazilian uranium mining and milling site located in a semi-arid region of the country. The process characterization demonstrated that in heap leach plants most of the 226Ra remains in the leached ore. Despite the potential higher availability of radium isotopes in the soils of the studied region the lack of precipitation in that area reduces the leaching/mobilization of the radionuclides. High 226Ra and 228Ra concentrations were found in manioc while 210Pb was significant in pasture. It was suggested that a range from 10(-3) to 10(-1) may conveniently encompass most of the transfer factors (TF) values for soil/plant systems (i.e. involving different cultures, different soils and natural radionuclides). Impacts due to aerial transportation of aerosols and radon generated in the mining were proved to be minimal and restricted to an area not greater than 15 km2. Finally, uranium complexation by carbonates was shown to be the main mechanism responding for the elevated radionuclide concentration in groundwater.     

Radioactivity concentration in liquid and solid phases of scale and sludge generated in the petroleum industry

Scales and sludge generated during oil extraction and production can contain uranium, thorium, radium and other natural radionuclides, which can cause exposure of maintenance personnel. This work shows how the oil content can influence the results of measurements of radionuclide concentration in scale and sludge. Samples were taken from a PETROBRAS unit in Northeast Brazil. They were collected directly from the inner surface of water pipes or from barrels stored in the waste storage area of the E&P unit. The oil was separated from the solids with a Soxhlet extractor by using aguarras at 90+/-5 degrees C as solvent. Concentrations of 226Ra and 228Ra in the samples were determined before and after oil extraction by using an HPGe gamma spectrometric system. The results showed an increase in the radionuclide concentration in the solid (dry) phase, indicating that the above radionuclides concentrate mostly in the solid material.     

Soil-to-plant transfer factors for natural radionuclides and stable elements in a Mediterranean area

The transfer factors (TF) for natural uranium isotopes (238U and 234U), thorium isotopes (232Th, 230Th and 228Th), and 226Ra were obtained in plant samples (grass-pasture) growing in granitic and alluvial soils around a disused uranium mine located in the Extremadura region in the south-west of Spain. Affected and non-affected areas of the mine presented large differences in the activity concentrations of radionuclides of the uranium series. We also determined transfer factors for several stable elements (essential and non-essential). A set of statistical tests were applied to validate the data. The results showed that the transfer factors for both the natural radionuclides and the stable elements are independent of the two substrate types involved and also of the two areas considered in the study.     

Environmental characterization and radio-ecological impacts of non-nuclear industries on the Red Sea coast

The Red Sea is a deep semi-enclosed and narrow basin connected to the Indian Ocean by a narrow sill in the south and to the Suez Canal in the north. Oil industries in the Gulf of Suez, phosphate ore mining activities in Safaga-Quseir region and intensified navigation activities are non-nuclear pollution sources that could have serious radiological impacts on the marine environment and the coastal ecosystems of the Red Sea. It is essential to establish the radiological base-line data, which does not exist yet, and to investigate the present radio-ecological impact of the non-nuclear industries to preserve and protect the coastal environment of the Red Sea. Some natural and man-made radionuclides have been measured in shore sediment samples collected from the Egyptian coast of the Red Sea. The specific activities of 226Ra and 210Pb (238U) series, 232Th series, 40K and 137Cs (Bq/kg dry weight) were measured using gamma ray spectrometers based on hyper-pure germanium detectors. The specific activities of 210Po (210Pb) and uranium isotopes (238U, 235U and 234U) (Bq/kg dry weight) were measured using alpha spectrometers based on surface barrier (PIPS) detectors after radiochemical separation. The absorbed radiation dose rates in air (nGy/h) due to natural radionuclides in shore sediment and radium equivalent activity index (Bq/kg) were calculated. The specific activity ratios of 228Ra/226Ra, 210Pb/226Ra, 226Ra/238U and 234U/238U were calculated for evaluation of the geo-chemical behaviour of these radionuclides. The average specific activity of 226Ra (238U) series, 232Th series, 40K and 210Pb were 24.7, 31.4, 427.5 and 25.6 Bq/kg, respectively. The concentration of 137Cs in the sediment samples was less than the lower limit of detection. The Red Sea coast is an arid region with very low rainfall and the sediment is mainly composed of sand. The specific activity of 238U, 235U and 234U were 25.3, 2.9 and 25.0 Bq/kg. The average specific activity ratios of 226Ra/228Ra, 210Pb/226Ra and 234U/238U were 1.67, 1.22 and 1.0, respectively. The relationship between 226Ra/228Ra activity ratio and sample locations along the coastal shoreline indicates the increase of this ratio in the direction of the Shuqeir in the north and Safaga in the south where the oil exploration and phosphate mining activities are located. These activities may contribute a high flux of 226Ra. The concentration and distribution pattern of 226Ra in sediment can be used to trace the radiological impact of the non-nuclear industries on the Red Sea coast.     

Natural radioactivity in some major rivers of coastal Karnataka on the southwest coast of India

Systematic studies on radiation level and distribution of radionuclides have been carried out in riverine environs of three major rivers of coastal Karnataka, viz. Kali, Sharavathi and Netravathi. The ambient gamma radiation levels along three rivers were measured using a portable plastic scintillometer. Activity concentrations of (226)Ra, (232)Th and (40)K in soil, sediment and rock were measured using a NaI(Tl) gamma-ray spectrometer. In the Kali, Sharavathi and Netravathi riverbanks, the median values of absorbed gamma dose rates in air were found to be 44 nGy h(-1), 35 nGy h(-1) and 57 nGy h(-1), respectively. The highest activity of (226)Ra was found in riverbank soil samples of Sharavathi River. The highest activities of (232)Th and (40)K were found in riverbank soil and sediment samples of Netravathi River. In Kali River, the highest (226)Ra activity was recorded for rock samples. To assess the radiological hazard of natural radioactivity in the samples, absorbed gamma dose rates in air, radium equivalent activity, representative level index, external hazard index and internal hazard index associated with the radionuclides were calculated and compared with internationally recommended values. The representative level index (I(gammar)) values are high in sediment samples of Netravathi River. The radium equivalent activity (Ra(eq)), external hazard index (H(ex)) and internal hazard index (H(in)) values are high in rock samples of Kali River. The results of these investigations are presented and discussed in this paper.     

Dissolution characteristics of 226Ra from phosphogypsum

The paper presents the results of the dissolution characteristics of 226Ra from phosphogypsum, a by-product from phosphate fertilizer industries. Leachability of 226Ra in distilled water and rainwater have been examined under different leaching conditions such as contact time, solid:liquid ratio and simulating natural conditions. The concentration of 226Ra activity in the leachates ranged from 0.07 to 0.53 Bq l(-1). Study indicated that leaching of radium may be slow in field conditions near the phosphogypsum stock piles.     

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.     

Influence of soil texture on the distribution and availability of 238U, 230Th, and 226Ra in soils

The influence of soil texture on the distribution and availability of (238)U, (230)Th, and (226)Ra in soils was studied in soil samples collected at a rehabilitated uranium mine located in the Extremadura region in south-west Spain. The activity concentration (Bqkg(-1)) in the soils ranged from 60 to 750 for (238)U, from 60 to 260 for (230)Th, and from 70 to 330 for (226)Ra. The radionuclide distribution was determined in three soil fractions: coarse sand (0.5-2mm), medium-fine sand (0.067-0.5mm), and silt and clay (<0.067 mm). The relative mobility of the natural radionuclides in the different fractions was studied by comparison of the activity ratios between radionuclides belonging to the same radioactive series. The lability of these radionuclides in each fraction was also studied through selective extraction from the soils using a one-step sequential extraction scheme. Significant correlations were found for (238)U, (230)Th, and (226)Ra between the activity concentration per fraction and the total activity concentration in the bulk soil. Thus, from the determination of the activity concentration in the bulk soil, one could estimate the activity concentration in each fraction. Correlations were also found for (238)U and (226)Ra between the labile activity concentration in each fraction and the total activity concentration in bulk soil. Assuming that there is some particle-size fraction that predominates in the process of soil-to-plant transfer, the parameters obtained in this study should be used as correction factors for the transfer factors determined from the bulk soil in previous studies.     

226Ra bioavailability to plants at the Urgeiriça uranium mill tailings site

Large amounts of solid wastes (tailings) resulting from the exploitation and treatment of uranium ore at the Urgeiri?a mine (north of Portugal) have been accumulated in dams (tailing ponds). To reduce the dispersion of natural radionuclides into the environment, some dams were revegetated with eucalyptus (Eucalyptus globolus) and pines (Pinus pinea). Besides these plants, some shrubs (Cytisus spp.) are growing in some of the dams. The objective of this study is to determine the 226Ra bioavailability from uranium mill tailings by quantifying the total and available fraction of radium in the tailings and to estimate its transfer to plants growing on the tailing piles. Plant and tailing samples were randomly collected and the activity concentration of 226Ra in plants (aerial part and roots) and tailings was measured by gamma-spectrometry. The exchangeable fraction of radium in tailings was quantified using one single step extraction with 1 mol dm-3 ammonium acetate (pH = 7) or 1 mol dm-3 calcium chloride solutions. The results obtained for 226Ra uptake by plants show that 226Ra concentration ratios for eucalyptus and pines decrease at low 226Ra concentrations in the tailings and appear relatively constant at higher radium concentrations. For shrubs, the concentration ratios increase at higher 226Ra solid waste concentrations approaching a saturation value. Percentage values of 16.0 +/- 8.3 and 12.9 +/- 8.9, for the fraction of radium extracted from the tailings, using 1 mol dm-3 ammonium acetate or calcium chloride solutions, respectively, were obtained. The 226Ra concentration ratios determined on the basis of exchangeable radium are one order of magnitude higher than those based on total radium. It can be concluded that, at a 95% confidence level, more consistent 226Ra concentration ratios were obtained when calculated on the basis of available radium than when total radium was considered, for all the dams.     

Diffusion of (226)Ra and (40)K radionuclides reproduced in underwater sedimentary columns in laboratory

The potential radiological impact of the increase of radioactive substances in the environment makes interesting the study of the migration of the contaminant radionuclides in soils and sediments, which are the last receiver system of these substances. By using a battery of sedimentary columns controlled in the laboratory, the diffusion of the (226)Ra and (40)K radionuclides has been studied, assessing their respective effective diffusion coefficients in a similar sedimentary medium. A decreasing temporal evolution is obtained, associated to the progressive 'fixation' of the radionuclides by the clay minerals of the sediment, followed by a constant tendency. A timescale of the 'fixation' by the sediment is determined, being of the order of days for (226)Ra and of the order of months for (40)K, so the progressive 'fixation' of (40)K by the clay minerals of the sediments is slower than in the case of (226)Ra.     

Nuclide migration and the environmental radiochemistry of Florida phosphogypsum

Phosphogypsum, a waste by-product derived from the wet process production of phosphoric acid, represents one of the most serious problems facing the phosphate industry in Florida today. This by-product gypsum precipitates during the reaction of sulfuric acid with phosphate rock and is stored at a rate of about 40 million tons per year on several stacks in central and northern Florida. The main problem associated with this material concerns the relatively high levels of natural uranium-series radionuclides and other impurities which could have an impact on the environment and prevent its commercial use. We have studied the potential release of radionuclides from phosphogypsum by: (i) analysis of stack fluids, groundwaters, and soils associated with gypsum stacks; and (ii) geochemical modeling. Stack fluids were observed to be very high in dissolved uranium and 210Pb with only moderate concentrations of 226Ra. Underlying soils tend to be enriched in U and 210Pb indicating precipitation when acidic stack fluids enter a buffered environment. Modeling results showed significant increases in radionuclide complexes with sulfate and phosphate, resulting in relatively mobile uncharged or negatively charged solution species within the stacks with likely precipitation of multicomponent solids with increasing pH below the stack. Our evidence thus suggests that, while phosphogypsum stacks do contain significant quantities of dissolved radionuclides, removal mechanisms appear to prevent large-scale migration of radionuclides to the underlying aquifer.     

Partitioning of radionuclides and trace elements in phosphogypsum and its source materials based on sequential extraction methods

Phosphogypsum is a waste produced by the phosphate fertilizer industry. Although phosphogypsum is mainly calcium sulphate dihydrate, it contains elevated levels of impurities, which originate from the source phosphate rock used in the phosphoric acid production. Among these impurities, radionuclides from 238U and 232Th decay series are of most concern due to their radiotoxicity. Other elements, such as rare earth elements (REE) and Ba are also enriched in the phosphogypsum. The bioavailability of radionuclides (226Ra, 210Pb and 232Th), rare earth elements and Ba to the surrounding aquatic system was evaluated by the application of sequential leaching of the phosphogypsum samples from the Brazilian phosphoric acid producers. The sequential extraction results show that most of the radium and lead are located in the "iron oxide" (non-CaSO4) fraction, and that only 13-18% of these radionuclides are distributed in the most labile fraction. Th, REE and Ba were found predominantly in the residual phase, which corresponds to a small fraction of the phosphate rock or monazite that did not react and to insoluble compounds such as sulphates, phosphates and silicates. It can be concluded that although all these elements are enriched in the phosphogypsum samples they are not associated with CaSO4 itself and therefore do not represent a threat to the surrounding aquatic environment.     

Sequential extraction of 226Ra in sediments from an estuary affected historically by anthropogenic inputs of natural radionuclides

Riverbed sediments from an estuary historically affected by wastes discharged by several phosphate fertiliser plants and enriched in uranium-series radionuclides were operationally speciated using a Tessier-based method. In each selective fraction the (226)Ra content was determined by alpha-particle spectrometry after radiochemical isolation and electrodeposition onto stainless steel planchets. These studies were performed in (226)Ra-polluted estuarine sediments collected one year after anthropogenic discharges had ceased in order to obtain useful information about the operational forms in which this radionuclide remains associated with the sediments at this time. The results obtained revealed that one year after (226)Ra inputs had stopped, the radionuclide was associated mostly with the more refractory forms. Consequently, it is possible to foresee little potential remobilisation of (226)Ra contamination from sediments to the aqueous phase in the future under normal environmental conditions.