Fractionation of plutonium in environmental and bio-shielding concrete samples using dynamic sequential extraction

Fractionation of plutonium isotopes (²³⁸Pu, ^239,240Pu) in environmental samples (i.e. soil and sediment) and bio-shielding concrete from decommissioning of nuclear reactor were carried out by dynamic sequential extraction using an on-line sequential injection (SI) system combined with a specially designed extraction column. Plutonium in the fractions from the sequential extraction was separated by ion exchange chromatography and measured using alpha spectrometry. The analytical results show a higher mobility of plutonium in bio-shielding concrete, which means attention should be paid to the treatment and disposal of nuclear waste from decommissioning.     

A novel approach to the sequential extraction of plutonium from oxic and anoxic sediment using sodium citrate to inhibit post-extraction resorption

Sequential extraction has been used extensively to study the solid partitioning of radionuclides in soils and sediments. A difficulty with sequential extraction is that radionuclides released by a particular extractant can be resorbed and artificially redistributed amongst the remaining solid phases. Here, we describe experiments (on selected model phase and natural materials), which were designed to determine whether the inclusion of a chelating agent (sodium citrate) in an established sequential extraction protocol (a) inhibits post-extraction resorption of plutonium, (b) increases non-targeted dissolution of sediment phases, and (c) gives rise to unwanted ligand competition for plutonium. The results clearly demonstrate the capacity of citrate to inhibit the resorption of plutonium from the various extractants, and confirm that there is no discernible increase in non-targeted phase dissolution, but indicate significant ligand competition with the carbonate phase. The merits of using citrate are discussed and an optimised sequential extraction protocol that includes citrate is proposed. Finally, the protocol is applied to oxic and anoxic sediments sampled in the NE Irish Sea and the Roads of Cherbourg, and it is shown that the bulk of the plutonium on these sediments is associated with the more labile geochemical fractions.     

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.     

A flow system for the determination of metal speciation in soil by sequential extraction

A flow extraction system with on-line and off-line flame atomic absorption spectrometric (FAAS) detection was developed to speed up, facilitate, and improve the accuracy of sequential extraction for metal speciation in solid materials. A flow extraction system with off-line detection was more advantageous than the on-line detection. In the proposed system, extraction was performed in a closed extraction chamber where extractants were flowing through sequentially. The extract from each extraction was collected in 4-10 fractions to obtain a total of approximately 180 ml for subsequent FAAS determination. The system is simple, easy to construct and operate. It has less risk of contamination and human error. A widely used three-step sequential extraction scheme was used to evaluate the novel system by analyzing Ca, Fe, Mn, Cu, and Zn in a certified reference material. The extraction time for three-step sequential extraction of soil sample was 4 h. The analytical results for Ca, Fe, Mn, Cu, and Zn of a soil certified reference material using the proposed system were compared with those of the conventional batch extraction.     

Importance of colloids in the transport within the dissolved phase (<450 nm) of artificial radionuclides from the Rhône river towards the Gulf of Lions (Mediterranean Sea)

The significance of colloidal fractions regarding the transport of artificial radionuclides in natural water systems is underlined by using sequential ultrafiltration both in the Rh?ne freshwater and the marine area under and outside the influence of the river outflow. Indeed, the Rhodanian aquatic system represents an interesting test site as various artificial radionuclides are released into the Rh?ne river by several nuclear installations. We focused our study on (137)Cs, (106)Ru, (60)Co, (238)Pu and (239+240)Pu. Our results show that Fe, Al and Organic carbon (OC) are the main components of colloidal matter. Colloids represent about 15% of dissolved (<450 nm) OC and 25% of dissolved Fe and Al exported towards the sea. Within the dissolved (< 450 nm) phase, these colloidal compounds are shown to account for the transport of 40% for both Co and Ru, 60% for (238)Pu and (239+240)Pu and have no significance on (137)Cs flux.     

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.     

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.     

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.     

Application of a magnetic extraction technique to assess radionuclide-mineral association in Cumbrian shoreline sediments

An assessment has been made of the association of (239+240)Pu, 241Am and 210Po (in secular equilibrium with 210Pb) with iron minerals using a magnetic extraction technique. Grab samples of beach sand from the Cumbrian (UK) coastline were subjected to successive extractions with an approximately 0.1 T ferrite magnet and an approximately 0.3 T rare-earth magnet procedure to separate magnetic iron oxide minerals. Radionuclide concentrations in the magnetic extracts were enhanced (by approximately 4-6-fold) relative to the residue. Those in the approximately 0.1 T magnet extracts were broadly similar to those in the antiferromagnetic material extracted by the approximately 0.3 T magnet, despite the very large differences in magnetic property values between the two fractions (one to two orders of magnitude). The percentage of magnetic material in terms of mass was small and therefore, the majority of these radionuclides (on average 88%) were associated with the residue. Removal of stable Fe was incomplete. Given that the radionuclides may also bind to paramagnetic (nonmagnetic) Fe minerals, the data were extrapolated by normalising the results to quantitative Fe removal. This yielded average values of 37%, 45% and 46% for (239+240)Pu, 241Am and 210Po(210Pb), respectively, as upper limits for the fraction associated with magnetic + nonmagnetic Fe minerals. There are significant uncertainties inherent in quantifying data from this extraction technique. Nevertheless, it seems reasonable to conclude that radionuclide association with Fe minerals is unlikely to have a significant impact upon the physical dispersion of sediment contaminated by Sellafield discharges in the Irish Sea. However, it may be an important factor in governing Pu redox and redissolution behaviour.     

Characteristics of soil organic matter (SOM) extracted using base with subsequent pH lowering and sequential pH extraction

Humic substances from eight soils of varying properties were extracted by two different methods: (1) the traditional NaOH-extraction with subsequent acidification to different pH (approximately 1 to approximately 12) and sequential extractions using 0.01 M NaNO(3) at incremental pH (approximately 1 to approximately 11). Cumulative organic matter (OM) in the sequential extractions showed properties that were consistent with NaOH-extracted OM. The release of Al and Fe in the sequential extractions was closely related with the release of organic carbon (OC). The ratio of OC associated with humic acid (HA) and fulvic acid (FA) (the HA:FA ratio) varied widely among the soils indicating heterogeneity in their OM composition. However, a significant correlation between this HA:FA ratio and the NaOH extractable %OC content of the soils is indicative of the possible relationship between them. Between pH 5 and 7, which is a typical soil solution pH, a significant amount of HA-associated OC was soluble. In modeling metal speciation in soil solutions, it has been assumed that all dissolved organic carbon (DOC) that is active toward metal binding is associated with FA. The results of this study indicate that the validity of these assumptions based on model sensitivity alone is questionable.     

Fractionation of natural radionuclides in soils from the vicinity of a former uranium mine ?irovski vrh, Slovenia

As a result of former uranium mining and milling activities at ?irovski vrh, Slovenia, 0.6 million tons of uranium mill tailings (UMT) were deposited onto a nearby waste pile Boršt. Resulting enhanced levels of natural radionuclides in UMT could pose threat for the surrounding environment. Therefore, sequential extraction protocol was performed to assess mobility and bioavailability of ²³⁸U, ²³⁴U, ²³⁰Th and ²²⁶Ra in soils from the waste pile and its surrounding. The radionuclides associated with exchangeable, organic, carbonate, Fe/Mn oxides and residual fraction, respectively, were determined. Results showed that the highest activity concentrations for the studied radionuclides were on the bottom of the waste pile. In non-contaminated locations, about 80% of all radionuclides were in the residual fraction. Considering activity concentrations in the UMT, ²³⁸U and ²³⁴U are the most mobile. Mobility of ²²⁶Ra is suppressed by high sulphate concentrations and is similar to mobility of ²³⁰Th.     

Deposition of gamma emitters from Chernobyl accident and their transfer in lichen-soil columns

Lichen-soil column samples were taken from several locations in the Southern Finland between 1986 and 2006. Columns were divided into three parts, upper lichen, lower lichen and underlying soil, and their gamma emitting radionuclides, (134)Cs, (137)Cs, (103)Ru, (95)Zr, (106)Ru, (110m)Ag, (125)Sb and (144)Ce, were measured with gamma spectrometry. Deposition values were calculated as Bq/m(2) for each sampling site. Distribution of various radionuclides in the three compartments as a function of time was determined. Both effective and ecological half-lives of all radionuclides were calculated for upper lichen, whole lichen and whole lichen-soil column. A linear relation was derived between the physical half-lives and effective half-lives for whole lichen and for whole lichen-soil column. Reindeer meat activity concentrations of various radionuclides and ensuing radiation doses to reindeer-herding people were also estimated for a hypothetical case where a similar high radioactive pollution, as was taken place in the Southern Finland, would have occurred in the reindeer-herding areas in the Finnish Lapland.     

Association of plutonium with sediments from the Ob and Yenisey Rivers and Estuaries

The present study applied sequential extraction techniques to investigate the binding and mobility of plutonium (Pu) in sediments from the rivers and estuaries of the Ob and Yenisey. As a study site, the Ob and Yenisey are particularly interesting as both rivers have weapons-grade Pu sources in their catchment areas, including the Russian Pu production and reprocessing plants at Mayak, Tomsk-7 and Krashnoyarsk, and the Semipalantinsk nuclear weapons testing site in Kazakhstan. Plutonium activity and ²⁴⁰Pu/²³⁹Pu ratios were determined using accelerator mass spectrometry (AMS). Sequential extractions showed that between 47 and 80% of the Pu in Yenisey River sediments and 35–53% of the Pu in soils around the Techa River are mobilized with weak oxidising agents, which can indicate that Pu is bound to organic material. In contrast, Pu in Ob and Yenisey Estuarine sediments was more strongly bound, with 60–100% being found in the HNO₃-extractable fraction. This change in speciation could reflect either that Pu bound to organic material in the Techa and Yenisey River sediments becomes more fixed to the sediments with time, or that organic-bound Pu is mobilized and released to the water when the sediments encounter the more saline water of the Ob and Yenisey estuaries. In general, ²⁴⁰Pu/²³⁹Pu ratios were relatively consistent between different extraction fractions, although, in whole sediments, an increase in ratio was observed with distance from the source. This reflects the increased influence of weapon fallout from catchment runoff within the river systems, as compared to the weapons-grade sources close to the production and reprocessing plants. Knowledge of Pu speciation in the Ob and Yenisey Rivers, and the processes controlling its behaviour in estuarine systems, can improve predictions of its transfer and subsequent environmental impact to Arctic Seas.     

Deposition of gamma emitters from Chernobyl accident and their transfer in lichen–soil columns

Lichen–soil column samples were taken from several locations in the Southern Finland between 1986 and 2006. Columns were divided into three parts, upper lichen, lower lichen and underlying soil, and their gamma emitting radionuclides, ¹³⁴Cs, ¹³⁷Cs, ¹⁰³Ru, ⁹⁵Zr, ¹⁰⁶Ru, ^110mAg, ¹²⁵Sb and ¹⁴⁴Ce, were measured with gamma spectrometry. Deposition values were calculated as Bq/m² for each sampling site. Distribution of various radionuclides in the three compartments as a function of time was determined. Both effective and ecological half-lives of all radionuclides were calculated for upper lichen, whole lichen and whole lichen–soil column. A linear relation was derived between the physical half-lives and effective half-lives for whole lichen and for whole lichen–soil column. Reindeer meat activity concentrations of various radionuclides and ensuing radiation doses to reindeer-herding people were also estimated for a hypothetical case where a similar high radioactive pollution, as was taken place in the Southern Finland, would have occurred in the reindeer-herding areas in the Finnish Lapland.     

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.     

Relationships between sea-bed radionuclide activities and some sedimentological variables

Natural radionuclides (232Th, 226Ra, 40K) and 137Cs, coming from atmospheric radioactive fallout, have been measured in sea-bed sediments of the Bay of Cádiz (South Western Spain). In this report, multivariate analysis methods have been employed to study the relationships between the activities of the radionuclides and some sedimentological variables like granulometric facies, organic content and apparent density. The correlation functions found show that it is possible to determine, with a satisfactory degree of approximation, the granulometric facies of the sediments using only radiometric information.     

Radioactive impact in sediments from an estuarine system affected by industrial wastes releases

A big fertilizer industrial complex and a vast extension of phosphogypsum piles (12 km2), sited in the estuary formed by the Odiel and Tinto river mouths (southwest of Spain), are producing an unambiguous radioactive impact in their surrounding aquatic environment through radionuclides from the U-series. The levels and distribution of radionuclides in sediments from this estuarine system have been determined. The analyses of radionuclide concentrations and activity ratios have provided us with an interesting information to evaluate the extension, degree and routes of the radioactive impact, as well as for the knowledge of the different pathways followed for the radioactive contamination to disturb this natural system. The obtained results indicate that the main pathway of radioactive contamination of the estuary is through the dissolution in its waters of the radionuclides released by the industrial activities and their later fixation on the particulate materials. Tidal activity also plays an important role in the transport and homogenization along the estuary of the radioactivity released from the fertilizer plants.     

A dynamic model for assessing radiological consequences of routine releases in the Loire river: parameterisation and uncertainty/sensitivity analysis

A dynamic model for assessing the transfer of several radionuclides ((58)Co, (60)Co, (110 m)Ag, (134)Cs, (137)Cs, (54)Mn and (131)I) in a food-chain was applied on the Loire river, where 14 nuclear power plants situated on five different sites operate. The model considers the following potential exposure pathways: (i) transfer of radionuclides through the aquatic food chain and the subsequent internal exposure of humans due to ingestion of contaminated water and/or fish; (ii) use of river water for agricultural purposes (irrigation), transfer of radionuclides through the terrestrial food chain and the subsequent internal exposure of humans due to ingestion of contaminated foodstuffs; (iii) internal exposure due to inhalation of dust originating from resuspension of contaminated soil particles; (iv) external exposure from radionuclides present in the river or deposited on the river sediments or the soil. For each of the parameters introduced in this model, a probability density function, allowing further uncertainty and sensitivity analysis, was proposed. Uncertainty/sensitivity analysis were performed to: (i) compare calculations to empirical data; (ii) determine a confidence interval for the mean annual dose to critical groups; and (iii) identify the parameters responsible for the uncertainty and subsequent research priorities.     

Distribution of organic carbon, selected stable elements and artificial radionuclides among dissolved, colloidal and particulate phases in the Rhône River (France): preliminary results

The behaviour of radionuclides discharged from nuclear facilities in the Rh?ne River depends on their distribution among the dissolved, colloidal and particulate phases. A large water sample was fractionated using sequential ultrafiltration. Size distributions of organic carbon, Fe, Al, Si, Ca, Mg, Cu, Zn, 137Cs, 60Co and 106Ru were obtained. Our results show that organic colloids account for 11% of the total organic carbon content. Approximately 20% of the dissolved (< 450 nm) Fe and Al are in colloidal classes. 137Cs is not significantly transferred by the colloidal phase while 25% of 60Co or 106Ru is associated with organic and inorganic colloids.     

Weather-dependent change of cesium, strontium, barium and tellurium contamination deposited as aerosols on various cultures

Various types of plants (wheat, bean, lettuce, radish and grass) were contaminated by dry deposition of radioactive aerosols ((137)Cs, (85)Sr, (133)Ba and (123 m)Te) in order to supplement the radio-ecological data necessary for operational post-accidental codes. A few days after deposition, rainfalls were applied to these cultures to evaluate the influence of some characteristics of the rain on the contamination of the culture over time. On the other hand, for wheat and bean, the influence of the humidity condition of the foliage at the contamination time was considered. For a given plant species at a given vegetative stage, the four radionuclides were intercepted in an identical way. The interception varied from 30% for bean (young sprout) to 80% for lettuce (near maturity). The global transfer factor values were dependent on both the radionuclides and the plant species; nevertheless, a higher value was obtained for cesium, regardless of the plant and the rainfall (from 0.006 m(2)kg(fresh)(-1) for wheat-grains - contaminated at the shooting stage - or for bean-pods - contaminated at the pre-flowering stage - to 0.1m(2)kg(fresh)(-1) for a whole lettuce). The analysis of the results allowed us on the one hand, to extract parameter values of the foliar transfer directly usable in operational codes, in particular those relating to barium and tellurium, unknown until then, and on the other hand, to lay the foundations of a future, more mechanistic model, taking into account the foliar processes in a finer way.