Federico Galan

In the SW of Spain, just in the confluence of the mouths of the Tinto and Odiel River and in the vicinity of Huelva town, there is a big industrial complex which includes between others an industry devoted during more than 40 years to the production of phosphoric acid, by treating sedimentary phosphate rock by the so-called "wet acid method". As a by-product of the mentioned process it have been produced historically huge amounts of a compound called phosphogypsum, which composition is mostly di-hydrate calcium sulphate containing some of the impurities of heavy metals and natural radionuclides originally present in the raw material. Due to the lack of market for this by-product, it has been mostly piled over some salt-marshes located in the vicinity of the industry, on the bank of the Tinto River. About 100 million tons of phosphogypsum have been piled in an area covering more than 1000 hectares, constituting a clear environmental and radiological anomaly in the zone. The...

ABSTRACT Liquid scintillation counting (LSC) is an easy and straightforward technique, and combined with its low limit of detection, makes it a powerful tool for both routine and low level measurements that can be applied to 210Pb low level counting in environmental samples. 210Pb can be easily measured following a sulphate co-precipitation method; the addition of a carrier and the weighing of the recovered amount is a widespread technique to evaluate radiochemical yield, however, this evaluation of the recovery is sometimes questioned. The samples employed in this work were recollected in 1999 and 2005 from the estuary of the Odiel and Tinto rivers (SW of Spain), which were affected by phosphogypsum (pg.) discharges until 1998. Phosphogypsum contains most of the 210Pb from the treated raw material, for that reason analysed riverbed sediments have enhanced 210Pb activity concentrations and hence, enhanced activity concentration of its daughter 210Po, both in secular equilibrium after two years.

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.

En el Capitulo 2 se hace una revision de los trabajos previos relacionados con nuestra investigacion. Pretendemos justificar el interes del problema que abordamos. ... : 12pt">En el Capitulo 3 se revisan los metodos radioquimicos empleados habitualmente para el analisis de 90Sr en distintos tipos de muestras ambientales. A continuacion se describe el metodo radioquimico utilizado por nosotros, los trabajos realizados para su desarrollo y puesta a punto y, por ultimo, los resultados (rendimiento quimico) obtenidos en las muestras analizadas.En el Capitulo 4 se describe el sistema detector, Quantulus 1220, utilizado para la determinacion de las concentraciones de 90Sr en las muestras analizadas. Se describen los trabajos de seleccion de los diversos parametros que inciden en la calidad de la medida o en su evaluacion. Un aspecto que se estudio en profundidad, y que se describe en este Capitulo, es la dependencia de la eficiencia de deteccion con el grado de color de la muestra. Tambien en el Capitulo 4 aparece una breve referencia al sistema de deteccion, y metodo de analisis, utilizado en la medida de 137Cs, y otros radionuclidos naturales, por espectrometria gamma.En el Capitulo 5 se describe la investigacion desarrollada en la plantacion de eucaliptos. Se distingue entres dos tipos de muestras: El suelo forestal y la vegetacion. En los dos casos se comienza describiendo la seleccion y recogida de muestras, su pretratamiento y los resultados de las medidas de las concentraciones de 137Cs y 90Sr. A continuacion se realizan diversos estudios comparativos entre los resultados obtenidos y diversos parametros fisicos y quimicos. Al final de este capitulo se expone la metodologia utilizada, para la evaluacion y los resultados obtenidos de los coeficientes de transferencia y flujos, correspondientes a los diversos compartimentos que hemos distinguido en la plantacion.La complejidad de la descripcion del funcionamiento de la fabrica de produccion de pasta de celulosa, y la consecuente interpretacion de los resultados obtenidos, nos ha llevado a optar por exponer en dos Capitulos independientes las investigaciones desarrolladas en la fabrica.En el Capitulo 6 se describe el proceso industrial y el funcionamiento de la fabrica de produccion de pasta de papel y se detallan las muestras recogidas, asi como su pretratamiento, para su estudio. En el Capitulo 7 se presentan los resultados obtenidos acerca de las concentraciones de radionuclidos en las muestras que consideramos representativas de los diferentes procesos que hemos distinguido en la fabrica. A continuacion se hace una evaluacion del flujo anual medio de 90Sr y 137Cs en la fabrica, comparandolo con elementos quimicos mayoritarios en los diferentes procesos y con radionuclidos naturales (fundamentalmente 40K) que se pueden considerar quimicamente semejantes. Finalmente se realiza una estimacion de los flujos de radionuclidos asociados a los vertidos generados en el proceso de produccion.Finalmente, en el Capitulo 8, se presentan las conclusiones mas importantes de esta memoria de Tesis.

Estuaries are sinks of materials and substances which are released directly into them or transported from rivers that drain the basin. It is usual to find high organic matter loads and fine particles in the sediments. We analyzed radionuclide concentrations ((210)Po, (230)Th, (232)Th, (234)U, (238)U, (226)Ra, (228)Th, (228)Ra, (40)K) in sediments and three different organs (roots, stems and leaves) of three species of halophytes plants (Spartina maritima, Spartina densiflora and Sarcocornia perennis). The study was carried out in two tidal salt marshes, one polluted by U-series radionuclides and another nearby that was unpolluted and was used as a control (or reference) area. The Tinto River salt marsh shows high levels of U-series radionuclides coming from mining and industrial discharges. On the contrary, the unperturbed Piedras River salt marsh is located about 25 km from the Tinto marsh, and shows little presence of contaminants and radionuclides. The results of this work have shown that natural radionuclide concentrations (specially the U-isotopes) in the Tinto salt marsh sediments are one order of magnitude higher than those in the Piedras marsh. These radionuclide enhancements are reflected in the different organs of the plants, which have similar concentration increases as the sediments where they have grown. Finally, the transfer factor (TF) of the most polluted radionuclides (U-isotopes and (210)Po) in the Tinto area are one order of magnitude higher than in the Piedras area, indicating that the fraction of each radionuclide in the sediment originating from the pollution is more available for the plants than the indigenous fraction. This means that the plants of the salt marshes are unhelpful as bioindicators or for the phytoremediation of radionuclides.

In this paper, (238)U-series radionuclides have been analysed in particulate matter samples collected at a phosphogypsum stack system located near the city of Huelva (SW Spain) during the course of 1 year. The results have been compared to those collected at a reference (background) site located a few km away, in order to establish if the stack system provokes an increase in radionuclide exposure due to inhalation with particulate matter. The (222)Rn progeny, which is considered a very important contributor to the internal dose rate received by the population, was collected for 6 months. The results indicate that for several types of radionuclides there is a significant increase in the radioactivity adsorbed by the aerosol particles collected at phosphogypsum stacks. The isotope analysis indicates that this increment could be affected by the water vapour emissions from the factory, which contain high concentrations of these radionuclides. However, the majority of these radionuclides...

The obtaining of phosphate fertilizers results in large amounts of residues that are frequently accumulated in deposits or pools occupying a wide area. These residues are acidic, and contain variable amounts of trace elements and radionuclides. The potentially polluting agents can be leached by rainwater, and so transferred to the surface waters and then to the groundwater after soil infiltration. Since the distribution and thickness of the residue deposits are variable, the contaminants cannot be easily traced back to a single, well defined source, and so a diffuse contamination (nonpoint source pollution) of the surrounding soils and waters occurs. This communication reports the results obtained in the study of soils close to the phosphogypsum deposits placed near Rio Tinto (Huelva, Spain). The zone is affected not only by the mentioned residues but also by the tides due to the vicinity of the sea. The samples studied had a low organic content and a low acidity with average values...

This paper presents a method for the determining 90Sr via its β-emitting daughter, 90Y, in environmental sam- ples by Cerenkov counting. The method is based on the isolation of 90Y by solvent extraction, using HDEHP as an extractor. The liquid scintillation (LS) analyzer Tri-Carb 3170 TR/SL has been employed. After radiochemical treatment, environmen- tal samples might be colored, and this

ABSTRACT Tropospheric ozone is considered one of the most significant air pollutants due to its negative effects on human health, agricultural crops, ecosystems and climate. The features of the southwest of the Iberian Peninsula (high temperatures and high solar radiation, the presence of the Guadalquivir basin and sources of precursors) favour the occurrence of episodes of high concentrations that cause exceedances of legal thresholds with relative frequency. Despite this, no study examining regional ozone episodes has been carried out in this region until now. In the present work a surface hourly ozone dataset (2003–2006) measured at 11 representative stations located in the southwest of the Iberian Peninsula (western Andalusia) was analysed in order to identify and characterise, for the first time, the regional ozone episodes that occur in this area. Using a statistical criterion, eight regional episodes were identified and analysed. The analysis of synoptic weather patterns revealed that these episodes occur in conjunction with two different synoptic conditions (high surface pressure either close to the British Isles or over the Atlantic Ocean). Both conditions generate weak isobaric surface pressure over the Iberian Peninsula, favouring the establishment of easterly winds at 500 m and the development of winds with two main prevailing directions (southwest-northwest, following the Guadalquivir basin) in the study area. During episodic days ozone follows a similar daily cycle to that observed on non-episode summer days, although the levels reached during the former are higher. In both cases, a direct relationship between the daily ozone cycle and the local wind regimen was not observed. This therefore seems to indicate that the daily cycle followed by ozone is mainly regulated by the precursor emissions produced in the environment, by the temperature changes taking place during the day and by the influence of the lower troposphere during anticyclonic weather conditions.

ABSTRACT 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 to Tinto and Odiel River had to be ceased.

Surface ozone is one of the most important photochemical pollutants in the low atmosphere, causing damage to human health, vegetation, materials and climate. The weather (high temperatures and high solar radiation), orography (presence of the Guadalquivir valley) and anthropogenic (the cities of Cádiz, Córdoba, Huelva and Seville and two important industrial complexes) characteristics of the southwestern Iberian Peninsula make this region ideal for the formation and accumulation of ozone. To increase the knowledge of ozone behaviour in this area, the monthly, daily and weekly variations of ozone and its precursors, nitrogen oxides (NO(x) = NO + NO2), were analysed over a 4-year period (2003 to 2006). Using the k-means cluster technique, 12 representative stations of five different areas with different ozone behaviour were selected from a total of 29 monitoring sites. This is the first time that the analysis of these atmospheric pollutants has been carried out for the whole area, allowing therefore a complete understanding of the dynamics and the relationships of these compounds in this region. The results showed an opposite behaviour among ozone and NO and NO2 concentrations in urban and suburban zones, marked by maximums of ozone (minimums NO(x)) in spring and summer and minimums (maximums) in autumn and winter. A seasonal behaviour, with lower amplitude, was also observed in rural and industrial areas for ozone concentrations, with the NO and NO2 concentrations remaining at low and similar values during the year in rural zones due to the absence of emission sources in their surroundings. The daily cycles of ozone in urban, suburban and industrial sites registered a maximum value in the early afternoon (14:00-17:00 UTC) while for NOx two peaks were observed, at 7:00-10:00 UTC and 20:00-22:00. In the case of rural stations, no hourly peak of ozone or NO(x) was registered. The weekend effect was studied by using a statistical contrast tests (Student's t). The results indicated that only areas influenced by important traffic emissions presented a weekend effect for NO and NO2, whereas an ozone weekend effect was not detected in any case.

This paper describes a comprehensive study of the behaviour of U in the Ría of Huelva estuary, formed by the Tinto and Odiel rivers. This ecosystem is conditioned by two hydrochemical facts: one connected with the acid mining drainage (AMD) generated in the first section of the river basins, and another one related to the fertilizer industry located at the estuary. AMD gives a singular character to these rivers; low pH and high redox potential that keep high amounts of toxic elements and radionuclides in dissolution. Most of the data for dissolved U in estuaries indicate conservative mixing, but there are examples of non-conservative behaviour attributed to oxidation/reduction processes or solubility variations. In the Ría of Huelva estuary the U shows a non-conservative behaviour due to solubility changes produced by variations in the pH. A complete removal of riverine dissolved U is observed in a pH range of 4-6. At higher pH values, U release from suspended matter, and probably also from sediments into the dissolved phase is found.

ABSTRACT Eucalyptus forests can be considered as the main source of raw material for the pulp industry of Spain. This environment was selected for a radioactivity study because natural and artificial radionuclides can be transferred into the pulp mills, associated with raw material, wood and barks, where they are concentrated by industrial processes, becoming a cause of doses. Radionuclide concentration of natural radionuclides (238U, 234U, 228Th, 230Th, 232Th) were determined by alpha- and gamma-spectrometry. Well-established radiochemical procedures were applied to environmental samples in order to isolate these radionuclides. A comparison between 228Th activity, determined by gamma-spectrometry, and 232Th activity, determined by alpha-spectrometry, was used as quality control parameter for analyses. The concentration factors were finally evaluated from experimental data.

In this paper a complete and self-consistent method for 90Sr determination in environmental samples is presented. It is based on the Cherenkov counting of 90Y with a conventional liquid scintillation counter. The effects of color quenching on the counting efficiency and background are carefully studied. A working curve is presented which allows to quantify the correction in the counting efficiency depending on the color quenching strength.

Artificial and natural radionuclides present in environmental samples (Eucalyptus wood and bark) can be transferred in an alkaline pulp mill and concentrated in the recycling process. Some part of the radionuclides can be released into the environment associated with the discharges from such a factory. An alkaline pulp mill located in the South of Spain was extensively sampled during 1993 and different radionuclides analysed in the collected samples. Thus the concentrations and fluxes of natural (40K, 226Ra, 228Ra and 228Th) and artificial (137Cs and 90Sr) radionuclides associated with the samples collected along the pulp production process are presented. It is shown that radium and thorium radionuclides behave similarly to strontium and calcium and, consequently, concentrate within the Ca-cycle. Furthermore, 40K and 137Cs are concentrated during the Na-cycle. Finally, the results obtained by the authors are compared with the levels found in similar factories, though situated in the North of Europe, by other researchers.

Long-lived artificial radionuclides (137Cs, 90Sr) were studied in a Eucalyptus plantation located in the south-west of Spain. Radionuclide concentrations were determined in different types of samples corresponding to specific forest components (soil, trees, herbs and litter). Depth profile distributions were obtained in two selected core soils. Two layers were separately measured in three other cores. The concentration factor, defined as the ratio between the mean activity concentration in a component and the mean activity concentration in the soil, was calculated for each component. The biomass of different components was estimated in order to evaluate the total density concentration (Bq/ha) of the artificial radionuclides (137Cs, 90Sr) in the Eucalyptus plantation. The transfer of the radionuclides between the different forest components can be inferred from the results. Additionally, other naturally occurring radionuclides (40K, 226Ra, 228Ra, 228Ac) were determined for comparison. Transport of radionuclides from forest to a nearby pulp mill is also discussed.

The determination of 90Sr in environmental samples can be done by using a gas-flow proportional counter (beta-counting) or a liquid-scintillation spectrometer (Cherenkov counting). In this work, we present the factor of merit (FOM) and the minimum detectable activity (MDA) for both the counters. Quantitative relationships are proposed for FOM and MDA determination.

The Tinto and Odiel rivers in southwest Spain drain the world's largest sulfide mineral formation: the Iberian Pyrite Belt which has been worked since 2,500 BC. The Tinto and Odiel estuarine zones include both an extensive area of salt marsh and an intensively industrialized urban area. As a consequence of pyrite oxidation, the Tinto and Odiel rivers are strongly acidic (pH < 3) with unusually high and quite variable metal concentrations. In this study, seasonally varying concentrations of dissolved major and trace elements were determined in the acid mine drainage affected estuary of the Ría de Huelva. During estuarine mixing, ore-derived metal concentrations exhibit excellent correlations with pH as the main controlling parameter. As pH increases, concentrations of dissolved ore-associated elements are attenuated, and this process is enhanced during the summer months. The decrease in Fe and Al concentrations ranged from 80 to 100 % as these elements are converted from dissolved to sediment-associated forms in the estuary. Coprecipitation/adsorption processes also removed between 60 and 90 % of the originally dissolved Co, Cu, Mn, Pb, Zn, and Th; however, Cd and Ni exhibited a greater propensity to remain in solution, with an average removal of approximately 60 %. On the other hand, As and U exhibited a different behavior; it is likely that these elements remain in dissolved forms because of the formation of U carbonates and soluble As species. Concentrations of As remain at elevated levels in the outer estuary (average = 48 μg L(-1)) which exceeds concentrations present in the Tinto River. Nevertheless, the estuary has recently witnessed improvements in water quality, as compared to results of several previous studies reported in the 1990s.