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In the salth-marshes of the Tinto River (Huelva estuary, SW Spain), are stored in stacks around 100 Mt of PG, covering a surface of 1000 ha without any type of isolation, which produce an important impact in the surrounding environment. On the other hand, this ecosystem it is affected by acid mine drainage (AMD) from sulphide mines located upstream the Tinto River. The aim of this study is to evaluate the deep pollution of the underlain salt-marsh sediments due to leachates from the PG stacks. For that purpose, 7 cores were collected from zones 2 and 3 of the stacks, and PG and salt-marsh sediments samples from different depths were analyzed. The physicochemical parameters, mineralogy, granulometry and the concentration of the main elements of interest were determined in the samples. Most analysed salt-marsh sediments are not affected by PG stacks pollution, because sediments act as a “barrier” for the leachates from the PG, concentrating the contaminants in the first decimetres (0.5 m) under PG-sediments contact, and the deep infiltration is very limited. The obtained results suggest that the perimeter channel which is projected to build in the restauration project, should has a depth of 1 m below the level of the PG stacks for assuring the complete collection of leachates from the stacks, and avoid their liberation into the Tinto River estuary.

Along the industrial process devoted to the production of titanium dioxide pigments by using ilmenite as main raw material, small residues amounts are generated, remaining clearly enriched in natural radionuclides and chemical pollutants. Between them, we can remark the scales enriched in both radium isotopes and lead, which are formed in the internal walls of pipes and some equipment. These scales are radiological anomalies that demand its mineralogical, elemental and radiometric characterization as a basis for a detailed radiological and toxicological assessment from the occupational and public point of view. In this work, several scales collected in a TiO2 pigment production plant in South of Spain have been mineralogically characterized by XRD, while information about their elemental composition and morphology have been obtained by applying the XRF and SEM techniques. In addition, radiometric determinations have been performed by gamma-ray and alpha-particle spectrometry. The performed study indicates that the radiological doses received due to the scales by the workers performing its conventional activities are clearly lower than 1 mSv/y. Special dosimetric and chemical controls could be needed for the workers in charge of the maintenance labours (which include the removal of the scales) if these workers belong to an external company devoted to perform maintenance operations in several NORM industries., This research was partially supported by the Spanish Government Department of Science and Technology (MINECO) through the project "Fluxes of Radionuclides Emitted by the Phosphogypsum Piles Located at Huelva; Assessment of the Dispersion, Radiological Risks and Remediation Proposals" (Ref. CTM 2015-68628- R), ), and the project of the Regional Government of Andalusia called “Basic processes regulating the fractionations and enrichments of natural radionuclides under acid mine drainage conditions” (Ref.: UHU-1255876) and the project of the University of Cadiz called "New methodogy of radioisotope isolation with environmental interest for its measurement by alpha spectrometry" (Ref: PR2019-024). The authors acknowledges to the staff of CITIUS at the University of Seville their help in the application of the X-ray techniques.

The accurate determination of the levels of 210Pb in environmental samples (e.g. atmospheric aerosols, waters, soils, biota, etc.) is essential due to its multiple applications in geochronology, radiation protection, groundwaters flows, air masses movement, etc. For this purpose, it has been developed a novel and thorough study of three alternative radiometric measuring methods of 210Pb activity concentrations in several types of samples. The three selected methods were low-level gamma spectrometry (210Pb), alpha-particle spectrometry (via 210Po), and Cherenkov counting (via 210Bi). This study has been performed in terms of precision, linearity and proportionality as well as spent time, type of matrix, and showing the most appropriate method of measure in each case. Several kinds of samples were analyzed such as atmospheric filters, soils, sediments and phosphogypsum (PG) matrices. These samples contain different 210 Pb activity concentrations and were measured by the three techniques carrying out radiochemical procedures when necessary. There were not significant differences in the results obtained for the samples analyzed by the three methods. The major precision was obtained by using alpha-particle spectrometry, but this method is more expensive and time consuming.

The regulation existing on NORM activities requires the accurate and quick measurement of natural radionuclides in a wide range of matrices by gamma spectrometry. The aim of this work has been to develop a comprehensive and accurate methodology to determine natural long-lived radionuclides (210Pb, 228,226Ra, 234,228Th and 40K) by gamma spectrometry with Ge detectors in NORM samples. An exhaustive calibration method to obtain the full-energy peak efficiency (FEPE), for each gamma emission energy, as a function of the thickness, apparent density and matrix composition of the cylindrical sample, has been developed. The selected certified calibration standards contain only natural radionuclides belonging to the 238U- and 232Th-series as well as 40K (codes RGU-1, RGTh-1 and RGK-1 from IAEA). Then, the obtained FEPE curves were validated using Genie 2000 simulations and Certified Reference Materials, for which the self-attenuation corrections were considered. Finally, a study on 222Rn losses was done for several samples.

The aim of this paper is to characterize two HPGe gamma-ray detectors used in two different laboratories for environmental radioactivity measurements, so as to perform efficiency calibrations by means of Monte Carlo Simulation. To achieve such an aim, methodologies developed in previous papers have been applied, based on the automatic optimization of the model of detector, so that the differences between computational and reference FEPEs are minimized. In this work, such reference FEPEs have been obtained experimentally from several measurements of the IAEA RGU-1 reference material for specific source-detector arrangements. The models of both detectors built through these methodologies have been validated by comparing with experimental results for several reference materials and different measurement geometries, showing deviations below 10% in most cases.

The industry devoted to the production of phosphoric acid by using as raw material sedimentary phosphate rock (PR) is considered as a NORM activity (Naturally Occurring Radioactive Materials), due to the high levels of U-series radionuclides contained in this ore, which are 1–2 orders of magnitude higher than those in unperturbed soils. This fact allowed us to develop a deep characterization of the raw materials, wastes, main intermediate materials, and final products obtained at a typical phosphoric acid factory. The elemental composition (major, minor and trace elements), radionuclide concentrations, grain size distribution, mineralogy and micro-structural composition were analyzed. The aim of this characterization was to obtain information for operators and maintenance personnel involved in clean-up and waste management operations. The highest concentrations of some heavy metals and radionuclide activity concentrations were found in the “scales” (or internal incrustations)from the pipes that carry either phosphoric acid (PA) or the phosphogypsum waste (PG). The highest concentrations where found for 226Ra and 40K,with values up to 9 and 5 Bq g−1, respectively. In addition, high concentrations of many toxic heavy metals and trace elements, such as Cd, Cr, Ni, Sr, Y, V, Zn, Th, and U, were found in some sludge samples. The shielding effect of the containers/vessels/pipes has an essential role in the measured external dose in the intermediate products. The radiological implications of natural radionuclides with higher activity showed that if the maximum particulate matter concentration established in the Spanish regulation is verified, and taking into account the most conservative scenario, the annual limit of 1 mSv y−1 is not exceeded.

Next to the city of Huelva (SW of Spain), around 100 Mt of phosphogypsum (PG) are stored in stacks on the salt-marshes of the Tinto River estuary covering a surface of about 1000 ha. Due to the high content of 238U series natural radionuclides of the PG, its acidic nature (pH about 3), and the fact that PG stacks were disposed without any kind of isolation from the substrate, they could produce a potential radioactive impact into the underlying sediments. The aim of this work is to assess the pollution of the underlying sediments by natural radionuclides coming from the PG stacks. To this end, seven cores were taken, and PG and sediments samples collected at different depths were analysed. The activity concentrations of the main long half-live natural radionuclides of interest were determined by applying both gamma-ray and alpha-particle spectrometry radiometric techniques. The results of this study showed that the first decimeters of salt-marsh sediment act as a “barrier” for the radionuclides coming from the PG stacks decreasing rapidly its activity concentration in depth, affecting mainly sediments located in the first 20 cm below the contact due to mixing processes. While 230Th, 226Ra and 210Pb pollution is mainly restricted to the first 20 cm of sediments, U-isotopes can reach higher depths (up to around 50 cm) by leaching processes due to their lower reactivity and higher concentration in the polluted leachates. The obtained results have high relevance for the design of the perimeter channel which is projected to build in the restoration project, suggesting that should has around 1 m deep under the base of the PG stacks, to ensure the full collection of polluting leachates, and to prevent their release into the estuary of the Tinto River.

Trabajo presentado al "EU NORM 2 Symposium" celebrado en Praga (República Checa) del 17 al 19 de junio de 2014., En programa: "Preliminary Steps in the Restoration of a Phosphogypsum Disposal Site: Radioactive Characterization of Leachates and Efflorescences Affecting the Surrounding Area"., After the recent closing of some phosphoric acid plants located in the South-West of Spain, it has been decided to restore a big extension (more than sixty hectares) of saltmarshes where historically some million tonnes of phosphogypsum (PG), the main byproduct generated by these plants, have been disposed of. This PG is characterized for containing high activity concentrations of several radionuclides from the uranium series, mainly 226Ra, 210Pb and 210Po and to a lesser extent U-isotopes. The PG disposal area can be considered as a potential source or radionuclides to their nearby environment, through the waters which percolate from them and through the efflorescences formed in their surroundings. A previous detailed radioactive characterization of the mentioned waters and efflorescences has been considered essential for a proper planification of the restoration plan to be applied in the near future in the zone.

The estuary formed by the confluence of Tinto and Odiel river‐mouths is located in the South of Spain, close to Huelva town. This estuary has been deeply studied through the years because it has a double particularity. On one hand, since the beginning of the 1960s, the estuary has been affected by direct and indirect phosphogypsum (pg.) releases from two phosphoric acid and fertilizers factories that are working in the area. On the other hand, the pyrite mining operations upstream the Odiel and Tinto rivers has caused historically the formation of H2SO4, through oxidation of the natural sulphur deposits, the acidification of the waters and the consequent mobilisation of heavy metals from the mining area to the Huelva estuary. As a consequence, enhancement contamination levels in natural emitters from the 238U series were found in the surroundings of the factories in the previous years to 1998. However, in 1998 the management policy of waste releases drastically changed in the area, and direct discharges t...