How the distribution coefficient of 238U in natural soils is affected by the method used to obtain the soil solution and its dependency on structural characteristics.

A systematic study on desorption of uranium in a natural soil has been carried out to reduce the level of uncertainty associated with the method employed to determine the values of the distribution coefficient (Kd). Generally, the operating method used to extract and analyze the soil solution determines the Kd values. Here, the centrifugation method has been used to obtain soil solution extracts. Several procedural parameters have been considered such as incubation time, the level of soil moisture relative to saturation (saturation degree) and centrifugation speed (equivalent to effective suction). In order to analyze the influence of soil structural characteristics, this study considers three grain-size fractions of soil: loamy coarse sand, loamy fine sand, and loam, all of which are obtained from a natural soil collected in a uranium mineralized area. Our results indicate that neither incubation time nor centrifugation speed influence the determination of Kd for uranium. The results also indicate that the level of soil moisture is the most important factor for determining 238U-Kd. It has been shown that the influence of moisture on Kd also depends on the structural characteristic of the soil. For the loamy coarse sand subsample, the moisture level during the incubation period showed a significant influence on the Kd. In addition, through the use of regression analysis, the pH was identified as the cofactor with the greatest influence on Kd of uranium.

Influence of soil conditions on the distribution coefficients of 226Ra in natural soils.

In order to clarify some of the assumptions and approximations about the use of the distribution coefficient Kd for 226Ra in soils, a systematic study has been performed using centrifugation to extract the soil solution. The separated fractions of the soil solution have different kinetics with respect to the sorption process in the soil, which may in turn condition the final chemical composition and even the speciation of the radionuclides in solution. In the experimental design of this study three factors were considered: the moisture level in the incubation process, incubation time and the speed of centrifugation. Also, three levels were chosen for each factor. In order to analyze the influence of the structural characteristics of the soil, this study was performed with three textural fractions: coarse sand, fine sand, and silt and clay, obtained from an only soil. Also, the soil was naturally enriched with radionuclides of the 238U series. An analysis of variance (ANOVA) was performed in order to assess the influence of the factors studied on the distribution coefficient of 226Ra. The results indicate that different behaviors can be observed depending on the structural characteristic of the soil. In the case of particle size, the soil with the largest grain size showed that the incubation process parameters influence the equilibrium level achieved, while in the case of the smallest edaphic particles, radium is not homogeneously distributed in the soil solution and the Kd value is dependent on the speed of centrifugation.

Influence of soil structure on the "Fv approach" applied to 238U and 226Ra.

The soil-to-plant transfer factors were determined in a granitic area for the two long-lived uranium series radionuclides 238U and 226Ra. With the aim to identify a physical fraction of soil whose concentration correlates linearly with the plant concentration, the soil compartment was analyzed in various stages. An initial study identified the soil compartments as being either bulk soil or its labile fraction. The bulk soil was subsequently divided into three granulometric fractions consisting of: coarse sand, fine sand, and silt and clay. The soil-to-plant transfer of radionuclides for each of these three texture fractions was analyzed. Lastly, the labile fraction was extracted from each textural part, and the activity concentration of the radionuclides 238U and 226Ra was measured. In order to assess the influence of soil texture on the soil-to-plant transfer process, we sought to identify possible correlations between the activity concentration in the plant compartment and those found in the different fractions within each soil compartment. The results showed that the soil-to-plant transfer process for uranium and radium depends on soil grain size, where the results for uranium showed a linear relationship between the activity concentration of uranium in the plant and the fine soil fraction. In contrast, a linear relation between the activity concentration of radium in the plant and the soil coarse-sand fraction was observed. Additionally, the presence of phosphate and calcium in the soil of all of the compartments studied affected the soil-to-plant transfer of uranium and radium, respectively.

Assessment of the vertical distribution of natural radionuclides in a mineralized uranium area in south-west Spain.

Low-level alpha spectrometry techniques using semiconductor detectors (PIPS) and liquid scintillation (LKB Quantulus 1220™) were used to determine the activity concentration of (238)U, (234)U, (230)Th, (226)Ra, (232)Th, and (210)Pb in soil samples. The soils were collected from an old disused uranium mine located in southwest Spain. The soils were sampled from areas with different levels of influence from the installation and hence had different levels of contamination. The vertical profiles of the soils (down to 40 cm depth) were studied in order to evaluate the vertical distribution of the natural radionuclides. To determine the origin of these natural radionuclides the Enrichment Factor was used. Also, study of the activity ratios between radionuclides belonging to the same radioactive series allowed us to assess the different types of behaviors of the radionuclides involved. The vertical profiles for the radionuclide members of the (238)U series were different at each sampling point, depending on the level of influence of the installation. However, the profiles of each point were similar for the long-lived radionuclides of the (238)U series ((238)U, (234)U, (230)Th, and (226)Ra). Moreover, a major imbalance was observed between (210)Pb and (226)Ra in the surface layer, due to (222)Rn exhalation and the subsequent surface deposition of (210)Pb.

Enhancing radium solubilization in soils by citrate, EDTA, and EDDS chelating amendments.

The effect of three chelating agents (citrate, EDTA, and EDDS) on the solubilization of radium from a granitic soil was studied systematically, considering different soil pH values, chelating agent concentrations, and leaching times. For all the chelating agents tested, the amount of radium leached proved to be strongly dependent on the pH of the substrate: only for acidic conditions did the amount of radium released increase significantly relative to the controls. Under the best conditions, the radium released from the amended soil was greater by factors of 20 in the case of citrate, 18 for EDTA, and 14 for EDDS. The greatest improvement in the release of radium was obtained for the citrate amendment at the highest concentration tested (50 mmol kg(-1)). A slightly lower amount of radium was leached with EDTA at 5 mmol kg(-1) soil, but the solubilization over time was very different from that observed with citrate or EDDS. With EDTA, a maximum in radium leaching was reached on the first day after amendment, while with citrate, the maximum was attained on the fourth day. With EDDS, radium leaching increased slightly but steadily with time (until the sixth day), but the net effect for the period tested was the lowest of the three reagents.

Improvement of a method for the sequential determination of 210Pb, 226Ra, and uranium isotopes by LSC and alpha-particle spectrometry.

In a previous paper the authors proposed a sequential method for the determination of isotopes of uranium, thorium, radium, and lead from environmental samples using alpha-particle spectrometry and LSC techniques. Although the radiochemical yields were suitable when the assays were performed on synthetic samples, application to real environmental samples caused a major decrease in the radiochemical yield, especially for uranium in inorganic samples (soils). A modification of the procedure is described that overcomes this drawback.

Enhancing uranium solubilization in soils by citrate, EDTA, and EDDS chelating amendments.

A systematic study was made of the effects of three soil amendments on the solubilization of uranium from a granitic soil. The aim was to optimize solubilization so as to enhance bioavailability for the purposes of remediation. The three amendments tested were with citrate, EDTA, and EDDS as chelating agents. The effects of pH, chelator concentration, and leaching time were studied. The most important factor in uranium solubilization was found to be the pH. In the absence of chelating agents, the greatest solubilization was obtained for alkaline conditions, with values representing about 15% of the total uranium activity in the bulk soil. There were major differences in uranium solubilization between the different amendments. The citrate treatment was the most efficient at acidic pH, particularly with the greatest concentration of citrate tested (50 mmol kg(-1)) after 6 days of treatment. Under these conditions, the uranium concentration in solution was greater by a factor of 356 than in the control suspension, and represented some 63% of the uranium concentration in the bulk soil. Under alkaline conditions, the EDTA and EDDS treatments gave the greatest uranium activity concentrations in solution, but these concentrations were much lower than those with the citrate amendment, and were not very different from the control results. The uranium extraction yield with EDDS amendment was greater than with EDTA.

Transfer of 238U, 230Th, 226Ra, and 210Pb from soils to tree and shrub species in a Mediterranean area.

The soil-to-plant transfer factors of natural uranium isotopes ((238)U and (234)U), (230)Th, (226)Ra, and (210)Pb were studied in a disused uranium mine located in the Extremadura region in the south-west of Spain. The plant samples included trees (Quercus ilex, Quercus suber, and Eucalyptus cameldulensis) and one shrub (Cytisus multiflorus). All of them are characteristic of Mediterranean environments. The activity concentrations in leaves and fruit were determined for the tree species at different stages of growth. For the shrub, the total above-ground fraction was considered in three seasons. For old leaves and fruit, the highest activity concentrations were found in Eucalyptus cameldulensis for all the radionuclides studied, except in the case of (230)Th that presented similar activity concentrations in all of the tree species studied. In every case, the transfer to fruit was less than the transfer to leaves. In the shrub, the results depended on the season of sampling, with the highest value obtained in spring and the lowest in autumn. Important correlations were obtained for (238)U and (226)Ra between the activity ratio in soils with that in leaves or fruit.

The ability of Helianthus annuus L. and Brassica juncea to uptake and translocate natural uranium and 226Ra under different milieu conditions.

Seedlings of Helianthus annuus L. (HA) and Brassica juncea (BJ) were used to test the effect of the pH, the presence of phosphates, and the addition of ethylene-diamine-tetraacetic acid (EDTA) or citrate on the uptake and the translocation of uranium isotopes ((238)U, (235)U, and (234)U) and (226)Ra. The results indicated that the presence of phosphates generally reduces the uptake and transfer of uranium from the roots to the shoots of HA. In the case of BJ, while phosphate enhanced the retention of uranium by roots, the translocation was poorer. Likewise, for (226)Ra, the best translocation was in the absence of phosphates for both species. The addition of citrate increased the translocation of uranium for both species, but had no clear effect on the transfer of (226)Ra. The effect of EDTA was much more moderate both for uranium and for (226)Ra, and for both plant species. Only noticeable was a slightly better uptake of (226)Ra by BJ at neutral pH, although the translocation was lower.

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.

Distribution of long-lived radionuclides of the 238U series in the sediments of a small river in a uranium mineralized region of Spain.

A study is presented on the distribution and mobilization of the natural U isotopes (238U and 234U), 230Th, and 226Ra in the sediments of a small river crossing an uranium mineralized zone where a disused uranium mine is located. Due to the preferential directions for surface run-off waters and to the mine's situation, one sampling point along the river bed was identified as a point of accumulation of radionuclides. The average values of the activity concentrations (Bq/kg) in this sediment sample were 5,025, 5,055, 5,915 and 1,694 for 238U, 234U, 230Th and 226Ra, respectively, while the respective average values of the activity concentrations (Bq/kg) for the sediment sample considered to give the background level were 125, 124, 131 and 370. Isotopic ratios between the descendants of 238U served to clarify some paths of distribution, involving the soils nearest to the sampling points and the location of these points with respect to the disused mine. The differences in behaviour found between the uranium, thorium and radium isotopes were associated to the mobility of these radionuclides in the fluvial system studied. Correlations between the radionuclide activity concentration ratios and stable element concentrations in the sediment samples were also investigated.

About the assumption of linearity in soil-to-plant transfer factors for uranium and thorium isotopes and 226Ra.

The linearity assumption for soil and plant concentrations of radionuclides is usually a good approximation for use in food-chain models. To verify this assumption, different samples of plant and substrate were collected from a granitic zone located near a disused uranium mine in order to cover a large range of concentrations. In all of the samples, the activity concentration of 226Ra and of different isotopes of uranium (238U and 234U) and thorium (232Th, 230Th and 228Th) were determined. The results indicate that the linearity assumption can be considered valid when the range of concentrations taken into account is large (approx. two orders of magnitude). Otherwise, there is a clear deviation from linearity. Also, the influence of different stable elements on the soil-plant transfer factors was studied by using multivariate regression methods. The uptake of uranium, thorium and radium was found to be mainly associated with the concentration of iron in the plant and the phosphorus and alkaline earths in the substrate.

Concerning the low uranium and thorium yields in the electrodeposition process of soil and sediment analyses.

The very low yields obtained in a common method of alpha-particle spectrometry for the determination of uranium and thorium in soil and sediment samples of environmental origin were investigated. Several experiments were performed to determine the cause. The results suggest that aluminium may cause major chemical interference in the electrodeposition process, and can be considered to be primarily responsible for the low recoveries found. A procedure is proposed to resolve this problem.

Radiological characterization of a uranium mine with no mining activity

We report a radiological study of a uranium mine located in Extremadura, in the south-west of Spain, in which mining work had ceased. One interest in the work is that the results can be used as a reference for the future evaluation of the effects produced by the restoration program. The radiological parameters selected to estimate the impact of the inactive mine were: 222Rn in air and water, 222Rn exhalation, effective 226Ra in soils and sediments, and natural uranium and 226Ra in water. Chemical analyses of water samples and measurements of meteorological variables were also made. Average values of these radiological parameters are presented. We characterize the zone radiologically and estimate the influence of the mine on the basis of some of these parameters, while others are used to reflect the status of the installation, information which could be very useful in the near future when restoration is complete.