Juan Mantero

Contamination and restoration of an estuary affected by phosphogypsum releases

The Huelva Estuary in Huelva, Spain, has been one of the most studied environmental compartments in the past years from the point of view of naturally occurring radioactive material (NORM) releases. It has been historically affected by waste releases, enriched in radionuclides from the U-decay series, from factories located in the area devoted to the production of phosphoric acid and phosphate fertilizers. Nevertheless, changes in national regulations forced a new waste management practice in 1998, prohibiting releases of phosphogypsum into the rivers. The input of natural radionuclides from phosphate factories to rivers was drastically reduced. Because of this there was a unique opportunity for the study of the response of a contaminated environmental compartment, specifically an estuary affected by tidal influences, after the cessation of the contaminant releases to, in this case, the Huelva Estuary (henceforth referred to as the Estuary). To investigate the environmental response to this new discharge regime, the specific activities of radionuclides 226Ra and 210Pb in water and sediment samples collected in four campaigns (from 1999 to 2005) were determined and compared with pre-1998 values. From this study it is possible to infer the most effective mechanisms of decontamination for the Estuary. Decontamination rates of 210Pb and 226Ra in the sediments and water have been calculated using exponential fittings and corresponding half-lives have been deduced from them. The cleaning half-life in the whole area of the Estuary is about 6 and 3.5 years for 226Ra and 210Pb respectively. The observed trend clearly shows that contamination of the Estuary by natural radionuclides is now decreasing and radioactive levels in waters and sediments are approaching the natural background references. This work attempts to evaluate whether it can be expected that the decontamination of the enhanced levels of natural radioactivity in the Estuary can be performed via natural processes.

Radiological, chemical and morphological characterizations of phosphate rock and phosphogypsum from phosphoric acid factories in SW Spain.

In this work, radiological, chemical, and also morphological characterization was performed in phosphate rock and phosphogypsum samples, in order to understand the behavior of toxic elements. Characterization was carried out using X-ray diffraction (XRD), X-ray fluorescence (XRF), gamma spectrometry and scanning electron microscopy with energy-dispersive X-ray analysis (SEM-EDX). Our results show that the phosphate rock was mainly composed of fluorapatite, calcite, perovskite, quartz, magnetite, pyrite and kaolinite, whereas phosphogypsum only exhibited dihydrated calcium sulfate. The activity concentration of U-series radioisotopes in phosphate rock was around 1640 Bq/kg. (226)Ra and (210)Pb tend to be distributed into phosphogypsum by up to 80%, whereas the fraction of U-isotopes is 10%. The most abundant trace elements in phosphate rock were Sr, Cr, V, Zn, Y, Ni and Ba. Some elements, such as Ba, Cd, Cu, La, Pb, Se, Sr, Th and Y, were enriched in the phosphogypsum. This enrichment may be attributed to an additional input associated to the sulfuric acid used for the phosphoric acid production. Furthermore, results from SEM-EDX demonstrated that toxic elements are not distributed homogeneously into phosphogypsum. Most of these elements are concentrated in particles <20 microm of high porosity, and could be easily mobilized by leaching and/or erosion.

Influence of the Fukushima Dai-ichi nuclear accident on Spanish environmental radioactivity levels

This paper presents measurements of the effect of the atmospheric radioactive release from the Fukushima Dai-ichi nuclear power station at three sites belonging to the Spanish environmental monitoring system. Measured values varied depending on the locations of the sites in Spain and their respective climatic characteristics. (134)Cs, (136)Cs, (137)Cs, (131)I, and (132)Te activity concentrations in filter samples were studied and associated levels of (131)I fallout were estimated from wet and dry deposition. Particulate aerosol activity concentrations ranges, in μBq/m(3), were 1.63-3080 ((131)I), 2.8-690 ((137)Cs), 1.3-620 ((134)Cs) and 3.6-330 ((132)Te), while the associated (131)I fallout was roughly estimated to be less than 20 Bq/m(2), Gaseous (131)I was also detected and the (131)I-gaseous/(131)I-total ratio increased at the three stations from approximately 0.75 at the end of March to 0.85-0.9 during the first few days of April. Finally, the presence of (131)I in some crucial parts of the food chain was also studied. (131)I was detected in samples from goats and cows milk (maximum levels of 1.11 Bq/L) and in broadleaf plants (maximum level 1.42 Bq/kg).

Radioactive characterization of leachates and efflorescences in the neighbouring areas of a phosphogypsum disposal site as a preliminary step before its restoration.

After the recent closure of certain phosphoric acid plants located in the South-West of Spain, it has been decided to restore a big extension (more than six hundred hectares) of salt-marshes, where some million tonnes of phosphogypsum (PG), the main by-product generated by these plants, had been disposed of. This PG is characterized by its content of high activity concentrations of several radionuclides from the uranium series, mainly (226)Ra, (210)Pb, and (210)Po and, to a lesser extent, U-isotopes. The PG disposal area can be considered as a potential source of radionuclides into their nearby environment, through the waters which percolate from them and through the efflorescences formed in their surroundings. For this reason, a detailed radioactive characterization of the mentioned waters and efflorescences has been considered essential for a proper planning of the restoration tasks to be applied in the near future in the zone. To this end, U-isotopes, (234)Th, (230)Th, (226)Ra, (210)Pb and (210)Po activity concentrations have been determined by applying both alpha-particle and gamma-ray spectrometric techniques to selected water and efflorescence aliquots collected in the area. The analysis of the obtained results has enabled to obtain information about the geochemical behaviour in the area of the different radionuclides analyzed; and the conclusion to be drawn that, in the restoration plan under preparation, both the prohibition of outflowing waters from the disposal area to the neighbouring salt-marshes, and the removal of all the efflorescences now disseminated in their surroundings are essential.

Determination of U and Th α-emitters in NORM samples through extraction chromatography by using new and recycled UTEVA resins.

This manuscript describes a protocol for the determination of U and Th isotopes via alpha spectrometry in NORM samples containing high concentrations of these radionuclides, up to kBq kg(-1). This technique is based on extraction chromatography with UTEVA (Triskem Int.) resins and it has been tested using both NORM samples from a phosphate industry and reference materials. The results proved that this method is highly optimized in terms of accuracy and precision when dealing with NORM samples. Recycling of UTEVA columns was also checked using NORM samples and successful results were obtained for both U and Th isotopes, thus proving the feasibility of re-using these type of columns.

Physico-chemical and radioactive characterization of TiO2 undissolved mud for its valorization.

In order to find a potential valorization of a waste generated in the industrial process devoted to the production of TiO(2) pigments, and as an essential and basic step, this waste must firstly be physically and chemically characterized. Moreover, the content of radioactivity is taken in to account due to it comes from a NORM (Naturally Occurring Radioactive Material) industry. With this end, microscopic studies were performed by applying scanning electron microscopy with X-ray microanalysis (SEM-XRMA), while the mineralogical compositions were carried out by means of the X-ray diffraction (XRD) technique. The concentrations of its major elements were determined by X-ray fluorescence (XRF), while heavy metals and other trace elements were ascertained through Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The results obtained for this waste have revealed several lines of research into potential applications. Firstly, with the refractory properties of mineral phases observed leading to a possible use in the ceramics industry or in thermal isolators. And secondly, attending to the characteristic particle-size spectra can be used as an additive in the manufacture of cement and finally, its high concentration of titanium may be used as a bactericide in brick production.

210Po and 238U isotope concentrations in commercial bottled mineral water samples in Spain and their dose contribution

(210)Po is a naturally occurring radionuclide, belonging to the uranium series, which is present in minute amounts in the different environmental compartments (water, soil, biota). Through its route along the trophic chain, it can be incorporated in the human body via ingestion of waters and/or food. This radionuclide is highly radiotoxic, being one of the main contributors to the committed effective dose via ingestion by the general population. In this work, the contribution of this radionuclide to the committed effective dose received by the Spanish population via consumption of bottled mineral waters is evaluated. With this end, the (210)Po activity concentrations in a total of 32 different commercial bottled mineral waters have been determined by alpha-particle spectrometry. The determined contribution is also compared with the contributions of other natural radionuclides such as (234)U and (238)U.

Uranium in the Surrounding of San Marcos-Sacramento River Environment (Chihuahua, Mexico)

The main interest of this study is to assess whether uranium deposits located in the San Marcos outcrops (NW of Chihuahua City, Mexico) could be considered as a source of U-isotopes in its surrounding environment. Uranium activity concentrations were determined in biota, ground, and surface water by either alpha or liquid scintillation spectrometries. Major ions were analyzed by ICP-OES in surface water and its suspended matter. For determining uranium activity in biota, samples were divided in parts. The results have shown a possible lixiviation and infiltration of uranium from geological substrate into the ground and surface water, and consequently, a transfer to biota. Calculated annual effective doses by ingestion suggest that U-isotopes in biota could not negligibly contribute to the neighboring population dose. By all these considerations, it is concluded that in this zone there is natural enhancement of uranium in all environmental samples analyzed in the present work.

Radiological impact of natural radionuclides from soils of Salamanca, Mexico

Salamanca is the centre of a large industrial complex associated with the production and refining of oil-derived products in the state of Guanajuato, Mexico. The city also hosts a large chemical industry, and in past years a major fertilizer industry. All of them followed NORM (naturally occurring radioactive materials) industrial activities, where either raw materials or residues enriched in natural radionuclides are handled or generated, which can have an environmental radiological impact on their environmental compartments (e.g. soils and aquatic systems). In this study, activity concentrations of radionuclides from the 238U and 232Th natural series present in superficial urban soils surrounding an industrial complex in Salamanca, México, have been determined to analyse the possible environmental radiological impact of some of the industrial activities. The alpha-particle and gamma-ray spectrometry is used for the radiometric characterization. The results revealed the presence of 10-42, 11-51 and 178-811Bq/kg of 238U, 232Th and 40K, respectively, without any clear anthropogenic increment in relation to the values normally found in unaffected soils. Thus, the radioactive impact of the industrial activities on the surrounding soils can be evaluated as very low, representing no radiological risk for the health of the population.

Radiological exposure assessment from soil, underground and surface water in communities along the coast of a shallow water offshore oilfield in Ghana

Radiometric determinations have been carried out to assess public exposure to radioactivity for communities along the coast of a shallow water offshore oilfield in Ghana (which started their operations recently) in order to establish baseline data using alpha spectrometry after radiochemical separation and non-destructive gamma spectrometry. The average activity concentrations of (234)U, (238)U, (230)Th and (232)Th by alpha-particle spectrometry and of (226)Ra, (228)Ra, (228)Th, (40)K, (210)Pb, (234)Th and (137)Cs by gamma-ray spectrometry were determined in the soil samples. The activity concentrations of (234)U, (238)U, (230)Th and (232)Th were determined in the water samples by alpha-particle spectrometry and of (226)Ra by liquid scintillation counting. The total annual effective dose to the public was estimated from the measured activity concentrations and this was clearly below the International Commission on Radiological Protection (ICRP) reference level of 1 mSv y(-1) for public exposure control. In addition, the estimated values of Raeq, Hex and Hin were all lower than the recommended acceptable values and the mean values of gross alpha and gross beta determinations performed for all the water samples give values that were all below the Ghana Standards Authority and World Health Organization recommended guideline values for drinking water quality. The results obtained show insignificant public exposure to radioactivity. However, this study provides important information for future studies on subsequent evaluations of the possible future environmental contamination due to activities of the oil industry in Ghana.