A methodology to determine 212Pb, 212Bi, 214Pb and 214Bi in atmospheric aerosols; Application to precisely obtain aerosol residence times and Rn-daughters' equilibrium factors.

Progeny of 222Rn and 220Rn, (212Pb, 212Bi, 214Pb and 214Bi) are essential to assess radiological hazard, external and internal doses, residence times and equilibrium factors. Precise measurements of these nuclides are quite complex due to their very short half-lives. This study outlines a new and precise methodology to measure these nuclides. Radon-222 and 220Rn were measured using a radon monitoring system, while their respective progenies were collected in an atmospheric filter using an ASS-500 sampler and measured by gamma-ray spectrometry. The 212Pb concentrations were very similar to the thoron ones, where all 212Bi/212Pb ratios were consistently less than 1. The relative uncertainties, σr, of the 212Pb and 212Bi activity concentrations, and 212Bi/212Pb activity ratio are generally less than 10%. Moreover, 214Pb/222Rn ratios were about 0.7, agreeing well with previous works. The σr for 214Pb, 214Bi and 214Bi/214Pb were generally less than 6%. This methodology was applied to estimate aerosol residence times using the 214Pb/222Rn and 212Bi/212Pb activity ratios, and to obtain equilibrium factors, achieving consistent results. Furthermore, the methodology consistency and validity range were studied with time elapsed between sampling end and counting start, and the sampling durations, finding the optimum times to precisely determine 212Pb, 212Bi, 214Pb and 214Bi.

An improved method for radium-isotopes quartet determination by alpha-particle spectrometry by using 225Ra (229Th) as isotopic tracer.

A new method for the determination of radium quartet (223,224,226,228Ra) in environmental samples by alpha-particle spectrometry with PIPS detectors is described. This uses 225Ra as yield tracer, in equilibrium at the beginning with 229Th. Thorium is removed from the sample by using AG1X8 anion-resin, and then radium isotopes are isolated and purified with a cation-exchange column Biorad AG50X8, verifying that Ac has been fully removed from the sample to ensure the good evaluation of the Ra yield (average decontamination factor > 92%). Finally, the counting source of radium is obtained by micro-precipitation with BaSO4. This method produces high spectral resolution (<35 keV), and quantitative Ra recoveries (>70%). In this new method, NH4Ac in 0.1 M HNO3 is used to remove the 225Ac contained in the sample in order to avoid its future spectral interference in the yield calculation. The method has been validated by using certified reference samples with known concentrations of radium isotopes.

Evidences of different meteorological patterns governing 7Be and 210Pb surface levels in the southern Iberian Peninsula.

7Be, 210Pb and PM10 levels in surface air have been simultaneously measured at two sampling sites in the southern Iberian Peninsula for a period of two years. Each site covers one different meteorological area of the Guadalquivir valley, from the mouth (Huelva) to the middle point (Cordoba). The objective of the present study is to analyse the spatial variability of both natural radionuclides, and to identify and characterise the meteorological patterns associated with similar and different surface concentration levels in this complex region. Concentrations are similar in both sampling sites. 7Be level is in the 0.6-15.5 mBq m-3 range in Huelva and 1.2-13.3 mBq m-3 in Córdoba, 210Pb activity concentrations are between 0.04 and 2.30 mBq m-3 in Huelva, and between 0.03 and 1.2 mBq m-3 in Cordoba, and PM10 concentrations are found to be in the 5.1-81.3 µg m-3 range in Huelva, and 8.2-76.3 µg m-3 in Cordoba, respectively. A linear regression analysis indicates more regional variability for 210Pb than for 7Be between simultaneous measurements. Principal components analysis (PCA) is applied to the datasets and the results reveal that aerosol behaviour is mainly represented by two components, which explain 82% of the total variance. The analysis of surface measurements and meteorological parameters revealed that component F1 groups sampling periods in which the influence of similar meteorological conditions over the region lead to similar 7Be, 210Pb and PM10 concentration levels in both sampling sites. On the other hand, component F2 detaches the 7Be, 210Pb and PM10 concentration levels between monitoring sites, and the meteorological analysis shows how surface concentrations within this component are associated with the development of different mesoscale circulations in each part of the valley. The identification of sampling periods characterised by differences in surface concentrations and wind patterns between stations suggests that the valley could not be considered as one single unit for certain meteorological scenarios. These results evidence how the understanding of wind characteristics within a complex terrain provide some essential knowledge in the regionalization and/or optimization of monitoring networks.

From floodplain to aquatic sediments: Radiogeochronological fingerprints in a sediment core from the mining impacted Sancho Reservoir (SW Spain).

The Sancho Reservoir (SW Spain) was built in 1962, about the time of maximum 137Cs fallout, and it has been affected by acid mine drainage (AMD) particularly since the mining cease in 2001. This is a unique scenario for studying the radiogeochronological fingerprints in AMD-affected sediments deposited over the former flood plain. A sediment core sampled in 2011 was analysed for bulk density, 137Cs, 239Pu, 240Pu, 210Pb, 226Ra, 228Ra, 234Th (238U) and 40K, and studied with various radiometric dating models. Bulk density revealed unsteady compaction and likely depositional events. The activity concentrations of 226Ra, 228Ra, 234Th (238U) and 40K were uniform down-core, but declining overall in the upper 0-25cm, revealing changes in provenance except for 238U, which increased in the top 10cm likely due to its supply by AMD. The AMD fingerprint was also found in the 239+240Pu/137Cs activity ratio, which increased in the top sediment layers. The 137Cs and 239+240Pu profiles show well defined peaks at the same depth, with inventories being about four times higher than the expected integrated atmospheric deposition in the area. The unsupported 210Pb (210Pbexc) showed a complex non-monotonic profile interrupted at several sections, particularly around the 137Cs peak. The whole dataset cannot be interpreted in terms of continuous sedimentation processes. Based upon correlated features in the bulk density and 210Pbexc profiles, a series of depositional events (likely linked to peaks in the rainfall records) have been identified in the core. These events date back to the period comprised since the construction of the dam until its increase in height in 1972, which likely displaced upstream the main depositional area of riverine loads, as inferred from sediment trap data. The CRS (with a reference date) and (a piecewise) CIC models have been used for complementing and discussing the chronology.

Water acidification trends in a reservoir of the Iberian Pyrite Belt (SW Spain).

Scarcity of waters is the main limiting factor of economic development in most arid and semi-arid regions worldwide. The construction of reservoirs may be an optimal solution to assure water availability if the drainage area shows low disturbances. This is the quandary of mining areas where economic development relies on water accessibility. Water acidification trends were investigated in the Sancho Reservoir (SW Spain) in the last 20 years. The acidity (pH3-5) and high dissolved metal concentrations (e.g., 4.4 mg/L of Al, 2.1mg/L of Mn, 1.9 mg/L of Zn) observed in the Sancho, together with the large volume stored (between 37 and 55 Mm(3)), makes this reservoir an extreme case of surface water pollution worldwide. A progressive acidification has been observed since 2003, as evidenced by decreasing pH values and increasing dissolved metal concentrations, especially noticeable after 2007. The increase in the net acidity in the reservoir originates from the higher input of metals and acidity due to the rebound effect after the mining closure in 2001. This trend was not detected in the river feeding the reservoir due to its great hydrological and hydrochemical variability, typical of the Mediterranean climate. Chemical analysis and absolute dating of sediments identified a progressive enrichment in S and metals (i.e., Fe, Zn Cu, Ni, Co and Cd) in the upper 20 cm, which reinforce the year 2002/03 as the onset of the acidification of the reservoir. The decrease of pH values from 4-5 to 3-4 occurred later than the increase in sulfate and metals due to pH-buffering by Al. The acid mine drainage (AMD) pressure has caused an increment of dissolved Fe and other metals, as well as a change in the pH buffering role, exerted now by Fe. These processes were simulated by PHREEQC, which confirms that the acidification trend will continue, causing pH values to reach 2.5 if AMD pressure persists.

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.

External radiation assessment in a wet phosphoric acid production plant.

The factories dedicated to the production of phosphoric acid by the so-called wet acid method are usually considered typical NORM industries, because the phosphate rock used as raw material usually contains high concentrations of (238)U-series radionuclides. The magnitude and behaviour of the radionuclides involved in the production process revealed the need to determine its dosimetric impact on workers. This work aims to partially compensate this lack of knowledge through the determination of external effective dose rates at different zones in the process at a typical plant located in the southwest of Spain. To this end, two dosimetric sampling campaigns have been carried out at this phosphoric acid production plant. The first sampling was carried out when phosphate rocks originating in Morocco were processed, and the second one when phosphate rock processed came from the Kola Peninsula (Russia Federation). This differentiation was necessary because the activity concentrations are almost one order of magnitude higher in Moroccan phosphate rock than in Kola phosphate rock. The results obtained have reflected external dose rate enhancements as high as 1.4microSvh(-1) (i.e., up to thirty times the external exposition due to radionuclides in unperturbed soils) at several points in the facility, particularly where the digested rock (pulp) is filtered. However, the most problematic points are characterised by a small occupation factor. That means that the increment in the annual effective external gamma dose received by the most-exposed worker is clearly below 1mSv (European Commission limit for the general population) under normal production. Nevertheless, special care in the design and schedule of cleaning and maintaining work in the areas with high doses should be taken in order to avoid any possibility of exceeding the previously mentioned general population limit. In addition, the results of the dosimetric campaign showed no clear correlation between (226,228)Ra activity concentrations in the material fluxing during the process (the most important radionuclides from the dosimetric point of view) and the external dose rates. Furthermore, any general dependence of the origin of the rock (i.e., on their radioactive contents) on the external effective dose rate measured has not been observed. These latter findings could be a consequence of three effects: (1) a variable radiation shielding at the different points along the process, (2) a changing geometry of irradiation (from a rock pile up to a thin-layered pulp passing through a solid mass inside pipes and deposits), and (3) the existence of a "memory effect", or background contamination in the installation equipment due to the presence of radionuclide-enriched scales and sludges in pipes and deposits.

A comparison between active and passive techniques for measurements of radon emanation factors.

Some radon related parameters have been determined through two different techniques (passive and active) in soil and phosphogypsum samples. Emanation factors determined through these techniques show a good agreement for soil samples while for phosphogympsum samples appear large discrepancies. In this paper, these discrepancies are analyzed and explained if non-controlled radon leakages in the passive technique are taken into account.

An assay on the effect of preliminary restoration tasks applied to a large TENORM wastes disposal in the south-west of Spain.

A large industrial wastes disposal site, where two phosphate rock processing plants release their wastes, located close to Huelva town (SW of Spain), has been partially submitted to restoration as a preliminary step in a possible decomissioning process. Due to the high natural radioactivity contents of these wastes, this repository is considered as a radiological anomaly, being actually considered as TENORM (technically enhanced naturally occurring radioactive materials). The efficiency of this restoration from the radiological point of view according to the new European regulatory framework was evaluated in this work. The results allow to conclude that, as a consequence of the partial restoration works, the external dose rate has been drastically reduced above the repository system. Nevertheless, special attention must be paid on the occupational factor to be applied to workers on the unrestored system. The application of a dosimetric model allows the prediction of the negative effects of using certain industrial wastes as a cover system in this restoration/mitigation task.

A semi-empirical approach for determination of low-energy gamma-emmiters in sediment samples with coaxial Ge-detectors.

A simple method for the determination in sediment samples of low-energy gamma-emitters with coaxial Ge detectors and using a cylindrical sample geometry is outlined. This method allows an easy estimation of self-absorption effects by knowing the apparent densities and the composition of the investigated samples. As calibration matrixes solid samples enriched in known amounts of natural radionuclides emitting low-energy gamma rays were used. In this way, the difficult homogenisation steps needed when liquid spikes are added to a solid blank for manufacturing the calibration sample are avoided. The method has been carefully checked and validated by applying it to sediment samples with known activities of some low-energy gamma-ray emitters. Additionally, these sediment measurements have allowed to evaluate the magnitude and importance of the self-absorption corrections.

Vertical distribution of Th-isotope ratios, 210Pb, 226Ra and 137Cs in sediment cores from an estuary affected by anthropogenic releases.

In an estuary system highly polluted by mining and industrial activities, the sections of sediment cores affected by anthropogenic inputs of U-series radionuclides (due to fertilizer plants releases) were determined through the vertical profiles of Th-isotopic ratio (230Th/232Th). Also, when possible, a modified version of the 210Pb dating method was applied in the uncontaminated sections of these cores. Using the information provided by the Th-isotopic ratio and 210Pb methods, we were able to establish confident chronologies, covering the last century, in several of the analysed sediment cores. These chronologies will be used in forthcoming research to study the time evolution of pollutant concentrations in the estuary. Additionally, and based on the established chronologies, we have found that sedimentation rates have drastically increased in some zones of the estuary since the commencement of several industrial activities in the surrounding environment and since the construction of two dikes in the area.

Validation of isotope signatures in sediments affected by anthropogenic inputs from uranium series radionuclides.

This paper aims to show the usefulness of 226Ra/228Ra activity ratios and confirm the possibility of using 230Th/232Th activity ratios as chronological markers in sediment cores from an estuarine system strongly contaminated by discharges from non-nuclear industries (fertiliser plants). The validation was carried out using an independent, well-established dating technique based on the analysis of the 137Cs fallout profile, which comprises the same time interval as that covered by both isotope ratios. The advantage of using the 226Ra/228Ra activity ratio profile instead of the Th-isotope profile is that determination can be accomplished with a non-destructive, simpler and less time-consuming technique, because both Ra isotopes can be determined by gamma-ray spectrometry.

230Th/232Th activity ratios as a chronological marker complementing 210Pb dating in an estuarine system affected by industrial releases.

The main purpose of this research is to show the usefulness of the 230Th/232Th activity ratios as a chronological marker that can be helpful in the dating of sediment cores collected from an estuarine system located in the south west of Spain highly polluted by wastes from fertilizer plants. These wastes, being released for 30 years, and enriched in radionuclides from the uranium series including 210Pb, invalidate the application of the 210Pb dating technique in full extent to the sediment cores collected in this estuary. However, the evaluation and the interpretation of both 210Pb and 230Th/232Th profiles allows the determination of average sedimentation rates in different parts of the cores, contaminated and noncontaminated zone, that agree in the case analysed in this research. Through this approach, a confident chronology covering the last century, which is essential to analyse and reconstruct the historical evolution of other pollutants in this heavily contaminated system can be established.

A dosimetric model for determining the effectiveness of soil covers for phosphogypsum waste piles.

Phosphogypsum (PG) is a by-product of the phosphoric acid production process that contains high concentrations of U-series radionuclides. PG piles formed during the last 30 years cover about 1,200 hectares and are located close to the town of Huelva (Spain) on a salt-marsh. The regional government of Andalusia restored the area beginning in 1990 by covering it with a 25-cm-thick layer of natural soil. With this restoration, the external gamma-dose rate in the zone has decreased drastically, approaching near environmental background values. This conclusion is based on results obtained through in-situ monitoring measurements and through a dosimetric model developed for that particular radiation source. As the model uses average parameters of the studied site, its output does not show a correlation point by point with the in-situ monitoring measurements. However, a good agreement is observed in average values over the covered piles. The model gives an average dose rate of 0.41 mGy y(-1) and the in situ monitoring 0.40 mGy y(-1). Based on this model, it is possible to calculate the necessary thickness of soil to reduce the dosimetric contribution from a similar extension of PG until the desired level is reached. In our conditions, in a 25-cm-thick soil, about 0.19 mGy y(-1) is the increase produced by the PG layer in relation to an infinitum soil layer. Consequently, no radiological concern exists in the restored zones with respect to the external gamma radiation.