R. García-Tenorio

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.

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.

ON THE FRACTIONATION OF NATURAL RADIOACTIVITY IN THE PRODUCTION OF PHOSPHORIC ACID BY THE WET ACID METHOD

The fractionation of different natural radionuclides (U-isotopes,226Ra and210Po) in the process used for the production of phosphoric acid in some factories located in the southwest of Spain is analyzed. As a consequence, different ways of natural radionuclide liberation to the environment can be evaluated due to these industrial activities.

Enhancement of natural radioactivity in soils and salt-marshes surrounding a non-nuclear industrial complex

The existence of a very high extension (about 1000 ha) of phosphogypsum piles, sited in the estuary formed by the mouths of the Tinto and Odiel rivers (SW Spain), produce a quite local, but unambiguous radioactive impact in the surrounding salt-marshes. In these piles the main by-product formed in the manufacture of phosphoric acid is stored. The radioactive impact is generated by the deposition and accumulation of radionuclides from the uranium series that previously had been mainly leached or dissolved from the piles by waters that temporally can cover or cross them. Other means of impact, especially through the atmosphere, have been evaluated as negligible or not detectable.

Behaviour and fluxes of natural radionuclides in the production process of a phosphoric acid plant

In recent years there has been an increasing awareness of the occupational and public hazards of the radiological impact of non-nuclear industries which process materials containing naturally occurring radionuclides. These include the industries devoted to the production of phosphoric acid by treating sedimentary phosphate rocks enriched in radionuclides from the uranium series. With the aim of evaluating the radiological impact of a phosphoric acid factory located in the south-western Spain, the distribution and levels of radionuclides in the materials involved in its production process have been analysed. In this way, it is possible to asses the flows of radionuclides at each step and to locate those points where a possible radionuclide accumulation could be produced. A set of samples collected along the whole production process were analysed to determine their radionuclide content by both alpha-particle and gamma spectrometry techniques. The radionuclide fractionation steps and enrichment sources have been located, allowing the establishment of their mass (activity) balances per year.

The cumulative effect of three decades of phosphogypsum amendments in reclaimed marsh soils from SW Spain : 226Ra, 238U and Cd contents in soils and tomato fruit

Phosphogypsum (PG), a by-product of the phosphate fertiliser industries, has been applied as soil amendment to reduce Na saturation in soils, as in the reclaimed marsh area from SW Spain, where available PG has a typical fingerprint of 710+/-40 Bq kg(-1) of (226)Ra, 165+/-15 Bq kg(-1) of (238)U and 2.8+/-0.4 mg kg(-1) of Cd. This work was focussed on the cumulative effects of PG amendments on the enrichment of these pollutants in cultivated soils and plants (Lycopersicum esculentum Mill L.) from the area studied, where PG has been applied since 1978 at recommended rates of 20-25 Mg ha(-1) every 2-3 years. A field experiment was conducted over three years to compare activity concentrations of (226)Ra ((214)Pb) and (238)U ((234)Th) in non-reclaimed soils, reclaimed soils with no additional PG application, and reclaimed soils with two additional PG applications. A non-significant effect of two PG amendments (in three years) was observed when compared with non-amended reclaimed plots. Nevertheless, a significant (p<0.05) enrichment of (226)Ra was observed in the surface horizon (0-30 cm) of reclaimed plots relative to deeper horizons and also when compared with the surface horizon of non-reclaimed soil (p<0.05), thereby revealing the cumulative effect of three decades of PG applications. Furthermore, the effect of a continuous application of PG was studied by analysing soils and tomato fruits from six commercial farms with different cumulative rates of PG applied. Cadmium concentrations in tomatoes, which were one order of magnitude higher than those found in tomatoes from other areas in South Spain, were positively correlated (r = 0.917) with (226)Ra-concentration in soils, which can be considered an accurate index of the cumulative PG rate of each farm.

210Pb determination by gamma spectrometry in voluminal samples (cylindrical geometry)

In this paper a simple method for the direct analysis of 210 Pb (T1=2 ¼ 22:3 years) by gamma-ray spectrometry in sediment samples with coaxial Ge detectors is outlined. This method, developed for a cylindrical sample geometry, accounts for variable sample heights and provides a fundamental advantage: individual self-absorption corrections can easily be determined knowingthe apparent densities of the samples. The results obtained with the proposed method are in good agreement with those given by other techniques. r 2002 Elsevier Science B.V. All rights reserved.

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.

Physicochemical characterization of raw materials and co-products from the titanium dioxide industry

The present study was conducted to characterize several raw materials and co-products from the titanium dioxide industry in relation to their elemental composition (major, minor and trace elements), granulometry, mineralogy, microscopic morphology and physical composition. The main objective was to gain basic information for the future potential application of these co-products in fields such as agriculture, construction, civil engineering, etc. Microscopic studies were performed by applying scanning electron microscopy with X-ray microanalysis (SEM-XRMA) while the mineralogical compositions were analysed by means of the X-ray diffraction (XRD) technique. The concentrations of major elements such as Na, Al, Si, Ca, Ti, Fe, S and K were determined by X-ray fluorescence (XRF), while heavy metals and other trace elements were determined by ICP-MS. The physicochemical characterization of the raw materials used in the titanium dioxide industry, in addition to the characterization of the co-products generated, has enabled the evaluation of the degree of fractionation of different elements and compounds between the different co-products, as well as the control of the possible variations in the physicochemical composition of the raw materials throughout the time and the study of the influence of these variations in the characteristics of the obtained co-products. As a main conclusion of our study, it is possible to indicate that the levels of the pollutant elements associated to the co-products analysed were, in general, within safe limits and, therefore, they could potentially be used in composites as fertilizers or for building materials in road construction, etc. Nevertheless, for the specific application of each of these co-products in agriculture, construction and civil engineering, additional studies need to be performed to evaluate their appropriateness for the proposed application, together with specific studies on their health and environmental impact.

Radioactivity contents in dicalcium phosphate and the potential radiological risk to human populations

Potentially harmful phosphate-based products derived from the wet acid digestion of phosphate rock represent one of the most serious problems facing the phosphate industry. This is particularly true for dicalcium phosphate (DCP), a food additive produced from either sulphuric acid or hydrochloric acid digestion of raw rock material. This study determined the natural occurring radionuclide concentrations of 12 DCP samples and 4 tricalcium phosphate (TCP) samples used for animal and human consumption, respectively. Metal concentrations (Al, Fe, Zn, Cd, Cr, As, Hg, Pb and Mg) were also determined. Samples were grouped into three different clusters (A, B, C) based on their radionuclide content. Whereas group A is characterized by high activities of 238U, 234U (approximately 10(3) Bq kg(-1)), 210Pb (2 x 10(3) Bq kg(-1)) and (210)Po ( approximately 800 Bq kg(-1)); group B presents high activities of (238)U, (234)U and (230)Th (approximately 10(3) Bq kg(-1)). Group C was characterized by very low activities of all radionuclides (< 50 Bq kg(-1)). Differences between the two groups of DCP samples for animal consumption (groups A and B) were related to the wet acid digestion method used, with group A samples produced from hydrochloric acid digestion, and group B samples produced using sulphuric acid. Group C includes more purified samples required for human consumption. High radionuclide concentrations in some DCP samples (reaching 2 x 10(3) and 10(3) Bq kg(-1) of 210Pb and 210Po, respectively) may be of concern due to direct or indirect radiological exposure via ingestion. Our experimental results based on 210Pb and 210Po within poultry consumed by humans, suggest that the maximum radiological doses are 11 +/- 2 microSv y(-1). While these results suggest that human health risks are small, additional testing should be conducted.