G. Manjón

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.

Study of colour quenching effects in the calibration of liquid scintillation counters: the case of 210Pb

Abstract In this work a rigorous method for the calibration of a liquid scintillation counter for 210 Pb activity determination is proposed. The variation of the PSA threshold level for alpha/beta discrimination with the colour quenching is analysed for different beta energies. Also the changes in some parameters of the detector response, as the muon-peak, the channel ratio and the centroid of the spectrum, due to colour quenching are studied. The relationship between such parameters and the counting efficiency is described in such a way that the effects of colour in the efficiency are established. 99 Tc is proposed as a good standard to calibrate the counter for 210 Pb determination in real samples.

Experimental and modelling study of plutonium uptake by suspended matter in aquatic environments from southern Spain.

Kinetic transfer coefficients are important parameters to understand and reliably model the behaviour of non-conservative radionuclides in aquatic environments. This report pertains to a series of five radiotracer experiments on Pu uptake in natural aqueous suspensions of unfiltered waters from three aquatic systems in the south of Spain (Gergal reservoir, the Guadalquivir river, and the estuary of the Tinto river). The experimental procedure ensured the simulation of environmental conditions. Pu activity was measured by a liquid scintillation technique. The uptake curves, covering a period up to one week, are discussed with respect to numerical uptake kinetics models. The data suggest that in our experimental setting the main pathways for Pu uptake consist of two parallel and reversible reactions followed by a consecutive non-reversible reaction. Kinetic transfer coefficients were estimated by a fitting procedure and a comparative study was followed.

Extensive radioactive characterization of a phosphogypsum stack in SW Spain: 226Ra, 238U, 210Po concentrations and 222Rn exhalation rate.

Phosphogypsum (PG) is a by-product of the phosphate fertilizer industries that contains relatively high concentrations of uranium series radionuclides. The US-EPA regulates the agriculture use of PG, attending to its (226)Ra content and to the (222)Rn exhalation rate from inactive stacks. Measurements of (222)Rn exhalation rates in PG stacks typically show a large and still poorly understood spatial and temporal variability, and the published data are scarce. This work studies an inactive PG stack in SW Spain of about 0.5 km(2) from where PG can be extracted for agriculture uses, and an agriculture soil 75 km apart, being representative of the farms to be amended with PG. Activity concentrations of (226)Ra, (238)U and (210)Po have been measured in 30 PG samples (0-90 cm horizon) allowing for the construction of maps with spatial distributions in the PG stack and for the characterization of the associated PG inputs to agriculture soils. Averaged (226)Ra concentrations for the stack were 730+/-60 Bq kg(-1) (d.w.), over the US-EPA limit of 370 Bq kg(-1). (222)Rn exhalation rate has been measured by the charcoal canister method in 49 sampling points with 3 canisters per sampling point. Values in PG stack were under the US-EPA limit of 2600 Bq m(-2)h(-1), but they were one order of magnitude higher than those found in the agriculture soil. Variability in radon emissions has been studied at different spatial scales. Radon exhalation rates were correlated with (226)Ra concentrations and daily potential evapotranspiration (ETo). They increased with ETo in agriculture soils, but showed an opposite behaviour in the PG stack.

Determination of 226Ra and 224Ra in drinking waters by liquid scintillation counting

A method for the determination of Ra-isotopes in water samples has been developed. Ra is coprecipitated with Ba as sulphate. The precipitate is then dissolved with EDTA and counted with a liquid scintillation system after mixing with a scintillation cocktail. The study of the temporal evolution of the separated activity gives the isotopic composition of the sample, i.e. the 224Ra and 226Ra contribution to the total activity. The method has been applied to some Spanish drinking waters.

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).

The presence of man-made radionuclides in the marine environment in the South of Spain

Abstract In this paper, levels of 137Cs, 99Tc, Pu-isotopes and 241Am in a wide group of seaweed species collected in the southern Spanish marine environment are given. Atmospheric fallout seems to be responsible for the presence of such radionuclides in the zone. However, it is shown that additional amounts of transuranic nuclides are present in the neighbouring coasts of Palomares. These are interpreted to be a consequence of the aircraft accident which occurred there during 1966.

99Tc/137Cs activity ratios in rainwater samples collected in the south of Spain

The presence of 99Tc and 137Cs in rainwater samples collected from 1984 to 1988 in the south of Spain has been studied. A simple model has allowed the description of the time evolution of the 99Tc/137Cs activity ratio. The calculated 99Tc stratospheric residence time, 1·62 ± 0·21 year, shows that the atmospheric behaviour of such a radionuclide is similar to that of other fission products. However, it could explain at the same time, the anomalous 99Tc/137Cs activity ratios obtained so far in the atmosphere. On the other hand, the appearance of Chernobyl-derived 137Cs activities in the south of Spain has been shown.

Application of a Liquid Scintillation Technique to the Measurement of 226Ra and 224Ra in Samples Affected by Non-Nuclear Industry Wastes

Experiment procedures have been developed for the determination of 226Ra and 224Ra activity concentration in solid and liquid samples collected around a non-nuclear industrial area, by liquid scintillation counting. The different radiochemical procedures developed in this work, have been adaptations of a radiochemical procedure previously used, for 226Ra and 224Ra determinations by LSC in drinking water, which was improved, refined up and adapted to the type of sample to be applied. These improved radiochemical methods have been applied to waste samples (phosphogypsum) produced by two factories which are engaged in phosphoric acid production, and to waters collected from the Odiel river, where during the sampling period a fraction of these wastes were released. 226Ra activity concentrations in the phosphogypsum ranged from 673 to 1178 Bq/kg dry weight, indicating that the wastes are particularly enriched in this radionuclide. Consequently, high 226Ra levels were easily found in the river waters analysed, especially in the neighbouring zones of the waste discharges.