Assessment of oral bioaccessibility of arsenic in playground soil in Madrid (Spain): A three-method comparison and implications for risk assessment

Three methodologies to assess As bioaccessibility were evaluated using playgroundsoil collected from 16 playgrounds in Madrid, Spain: two (Simplified Bioaccessibility Extraction Test: SBET, and hydrochloric acid-extraction: HCl) assess gastric-only bioaccessibility and the third (Physiologically Based Extraction Test: PBET) evaluates mouth–gastric–intestinal bioaccessibility. Aqua regia-extractable (pseudo total) As contents, which are routinely employed in riskassessments, were used as the reference to establish the following percentages of bioaccessibility: SBET – 63.1; HCl – 51.8; PBET – 41.6, the highest values associated with the gastric-only extractions. For Madridplaygroundsoils – characterised by a very uniform, weakly alkaline pH, and low Fe oxide and organic matter contents – the statistical analysis of the results indicates that, in contrast with other studies, the highest percentage of As in the samples was bound to carbonates and/or present as calcium arsenate. As opposed to the As bound to Fe oxides, this As is readily released in the gastric environment as the carbonate matrix is decomposed and calcium arsenate is dissolved, but some of it is subsequently sequestered in unavailable forms as the pH is raised to 5.5 to mimic intestinal conditions. The HCl extraction can be used as a simple and reliable (i.e. low residual standard error) proxy for the more expensive, time consuming, and error-prone PBET methodology. The HCl method would essentially halve the estimate of carcinogenic risk for children playing in Madridplaygroundsoils, providing a more representative value of associated risk than the pseudo-total concentrations used at present

De plagios, planos y vistas urbanas: Nueva Mantua Carpetanorum, de Pieter van den Berge

Uno de los méritos de este plano es el constituir la primera copia, hasta ahora conocida, del Mantua Carpetanorum sive Matritum, Urbs Regia, del portugués Pedro Texeira, editado en Amberes en 1656 (1) . Otro, el de formar parte de una de las primeras compilaciones de estampas españolas realizadas a finales del siglo XVII, el Theatrum hispaniae exhibens regni urbes, villas ac viridaria magis illustria. Plano y compilación son obra del dibujante, grabador y editor holandés Pieter van den Berge

La geoquímica de los sedimentos de llanuras de inundación como guía para la valoración ambiental en España

En la presente tesis se estudian los contenidos geoquímicos de los sedimentos de llanura de inundación en diversas cuencas fluviales seleccionadas con el objetivo de contribuir a un mejor conocimiento de sus condiciones medioambientales. En cada cuenca, se ha muestreado un perfil vertical de llanura de inundación, dividiéndolo en tramos que generalmente corresponden a diferentes episodios de inundación. Estos sedimentos se depositan durante los episodios de crecidas una vez que la corriente sobrepasa los límites del canal. Se caracterizan normalmente por tener un tamaño de grano fino y una estructura en capas horizontales que corresponden a los sucesivos episodios de inundación. Muestran dos ventajas principales con respecto a otros medios de muestreo en geoquímica como suelos o sedimentos de corriente: • Pueden almacenar sedimento antiguo así como actual, con lo que se puede estudiar la historia geoquímica de una zona específica en un mismo punto de muestreo (perfil vertical). • Los sedimentos de llanuras de inundación son capaces de caracterizar grandes áreas de drenaje. El origen de los sedimentos es más diverso que en el sedimento de corriente, debido a las mayores áreas de donde proceden las aguas de las avenidas. Las cuencas han sido seleccionadas según las actividades antropogénicas que en ellas se llevan a cabo, en concreto, actividades urbanas e industriales, minería y agricultura. Así mismo, se han estudiado, como referencia, dos cuencas donde no se espera encontrar ningún tipo de actividad contaminante. Una vez hecha la selección, los sedimentos aluviales de las cuencas se han estudiado cuidadosamente para asegurar que no existen depósitos de acreción lateral en el punto seleccionado. Posteriormente se ha procedido al muestreo del perfil vertical. Las muestras han sido analizadas mediante ICP-MS (ataque total) e INAA para conocer los contenidos totales de los elementos traza y mayoritarios. Los análisis de la fracción extraíble se han llevado a cabo mediante ICP-MS (ataque con agua regia). Así mismo, algunas muestras seleccionadas han sido sometidas a una extracción secuencial para un estudio más detallado. La presencia de materia orgánica ha sido estimada mediante el análisis de Carbono Orgánico Total (TOC). Finalmente, se ha llevado a cabo un análisis de isótopos de Pb en muestras escogidas en los perfiles, con el objetivo de hacer una evaluación ambiental. Los contenidos metálicos aumentan hacia la superficie en algunos de los perfiles, mientras en otros muestran una distribución muy constante exceptuando algún nivel específico con un aumento de los contenidos de la mayoría de los metales. Ha sido posible determinar la influencia de las actividades antropogénicas en algunos de los perfiles. Aquellos que pertenecen a cuencas mineras, urbanas o industrializadas muestran generalmente altos contenidos en elementos metálicos. Es el caso de los perfiles muestreados en los ríos Odiel y Tinto, Besaya, Besós y Manzanares. Algunos de estos perfiles pueden incluso correlacionarse con periodos de tiempo en los que ha tenido lugar una actividad antropogénica más intensa. Los perfiles que mejor se correlacionan con la actividad antropogénica de la cuenca son el perfil de Rivas en el río Manzanares (Madrid), que refleja un crecimiento de la contaminación producida por las actividades urbana e industrial en las últimas décadas, y el río Tinto, que muestra un crecimiento llamativo de los contenidos en su mayoría metálicos que puede estar relacionado con el incremento de la actividad minera que tuvo lugar hace aproximadamente 125 años. El análisis de los isótopos de Pb ha resultado ser una herramienta útil en la evaluación ambiental de estos sedimentos. Con este estudio y mediante la comparación con fuentes naturales y antropogénicas, ha sido posible diferenciar las muestras afectadas por diferentes fuentes de plomo, así como detectar las más afectadas antropogénicamente. ABSTRACT The geochemical composition of overbank sediments of some selected river basins is studied in this thesis in order to contribute to a better knowledge of the environmental conditions surrounding them. In each basin a vertical overbank profile has been sampled, dividing it into stretches that usually correspond to different flood events. The overbank sediments are those deposited during a flood event once the flow spills over the channel banks. They are usually characterized by a very fine grain size and a structure of horizontal layers, which correspond to successive flood events. These sediments show two main advantages regarding other sampling media in geochemistry, like soils or stream sediments: • They can store sediment deposited in the past as well as in current times, so that the history of a specific location can be studied at the very same point (vertical profile). • The overbank sediments are able to characterize a large drainage area. The origin of the sediment is wider than in the stream sediments due to the larger areas where the flood water comes from. The basins have been selected depending on the anthropogenic activities developed in them, namely, urban and industrial activities, mining activities and agricultural activities. As well, two pristine basins have been studied as a reference. Afterwards, the alluvial sediments in the basins have been carefully studied in order to sample a vertical profile and make sure that lateral accretion materials are not present in the profile. The samples have been analysed by ICP-MS (total digestion) and INAA to know the total contents of trace and major elements. Analysis of the mobile fraction has been carried out by ICP-MS (aqua regia); as well some of the samples have been subjected to sequential extraction for a more detailed study. The presence of organic matter has been estimated by the analysis of the Total Organic Carbon (TOC). Finally, a lead isotope analysis of some of the samples in the profiles was carried out in order to make an environmental assessment. Metal contents grow towards the surface in some of the profiles, while others show a very steady distribution, except for some of them with a growth of most of the metals in a specific level. XI It has been possible to determine the influence of the anthropogenic activities in some of the profiles. The ones that belong to mining and urban or industrialized basins show generally high contents of metal elements. This is the case of the profiles sampled in the Odiel and Tinto Rivers, the Besaya River, the Besós River and the Manzanares River. Some of these profiles can even correlate with the periods of time when a more intense activity in their respective basins has taken place. The profiles which best correlate with the anthropogenic activity are the Rivas profile in the Manzanares River, which reflects a growth of the pollution produced by urban and industrial activities in the city of Madrid in the last decades and the Tinto profile, which shows a very dramatic growth of the elemental contents (mostly metals) which can be related to the increase of the mining activities that took place in the last 125 years. The analysis of lead isotopes has turned out to be a powerful tool in the environmental assessment in this type of sediments. With this study and through the comparison with natural and anthropogenic sources, it has been possible to determine samples affected by different sources of lead and to detect the most anthropogenicaly affected ones.

The relationship between soil geochemistry and the bioaccessibility of trace elements in playground soil

A total of 32 samples of surficial soil were collected from 16 playground areas in Madrid (Spain), in order to investigate the importance of the geochemistry of the soil on subsequent bioaccessibility of trace elements. The in vitro bioaccessibility of As, Co, Cr, Cu, Ni, Pb and Zn was evaluated by means of two extraction processes that simulate the gastric environment and one that reproduces a gastric + intestinal digestion sequence. The results of the in vitro bioaccessibility were compared against aqua regia extractions (“total” concentration), and it was found that total concentrations of As, Cu, Pb and Zn were double those of bioaccessible values, whilst that of Cr was ten times higher. Whereas the results of the gastric + intestinal extraction were affected by a high uncertainty, both gastric methods offered very similar and consistent results, with bioaccessibilities following the order: As = Cu = Pb = Zn > Co > Ni > Cr, and ranging from 63 to 7 %. Selected soil properties including pH, organic matter, Fe and CaCO3 content were determined to assess their influence on trace element bioaccessibility, and it was found that Cu, Pb and Zn were predominantly bound to organic matter and, to a lesser extent, Fe oxides. The former fraction was readily accessible in the gastric solution, whereas Fe oxides seemed to recapture negatively charged chloride complexes of these elements in the gastric solution, lowering their bioaccessibility. The homogeneous pH of the playground soils included in the study does not influence trace element bioaccessibility to any significant extent except for Cr, where the very low gastric accessibility seems to be related to the strongly pH-dependent formation of complexes with organic matter. The results for As, which have been previously described and discussed in detail in Mingot et al. (Chemosphere 84: 1386–1391, 2011), indicate a high gastric bioaccessibility for this element as a consequence of its strong association with calcium carbonate and the ease with which these bonds are broken in the gastric solution. The calculation of risk assessments are therefore dependant on the methodology used and the specific environment they address. This has impacts on management strategies formulated to ensure that the most vulnerable of society, children, can live and play without adverse consequences to their health.

Geochemistry and risk assessment of street dust in Luanda, Angola, a tropical urban environment

A total of 92 samples of street dust were collected in Luanda, Angola, were sieved below 100 μm, and analysed by ICP-MS for 35 elements after an aqua-regia digestion. The concentration and spatial heterogeneity of trace elements in the street dust of Luanda are generally lower than in most industrialized cities in the Northern hemisphere. These observations reveal a predominantly “natural” origin for the street dust in Luanda, which is also manifested in that some geochemical processes that occur in natural soils are preserved in street dust: the separation of uranium from thorium, and the retention of the former by carbonate materials, or the high correlation between arsenic and vanadium due to their common mode of adsorption on solid particles in the form of oxyanions. The only distinct anthropogenic fingerprint in the composition of Luanda's street dust is the association Pb–Cd–Sb–Cu (and to a lesser extent, Ba–Cr–Zn). The use of risk assessment strategies has proved helpful in identifying the routes of exposure to street dust and the trace elements therein of most concern in terms of potential adverse health effects. In Luanda the highest levels of risk seem to be associated (a) with the presence of As and Pb in the street dust and (b) with the route of ingestion of dust particles, for all the elements included in the study except Hg, for which inhalation of vapours presents a slightly higher risk than ingestion. However, given the large uncertainties associated with the estimates of toxicity values and exposure factors, and the absence of site-specific biometric factors, these results should be regarded as preliminary and further research should be undertaken before any definite conclusions regarding potential health effects are drawn.

Geochemical fingerprints and controls in the sediments of an urban river: River Manzanares, Madrid (Spain)

The geochemical fingerprint of sediment retrieved from the banks of the River Manzanares as it passes through the City of Madrid is presented here. The river collects the effluent water from several Waste Water Treatment (WWT) plants in and around the city, such that, at low flows, up to 60% of the flow has been treated. A total of 18 bank-sediment cores were collected along the course of the river, down to its confluence with the Jarama river, to the south–east of Madrid. Trace and major elements in each sample were extracted following a double protocol: (a) “Total” digestion with HNO3, HClO4 and HF; (b) “Weak” digestion with sodium acetate buffered to pH=5 with acetic acid, under constant stirring. The digests thus obtained were subsequently analysed by ICP-AES, except for Hg which was extracted with aqua regia and sodium chloride-hydroxylamine sulfate, and analysed by Cold Vapour-AAS. X-ray diffraction was additionally employed to determine the mineralogical composition of the samples. Uni- and multivariate analyses of the chemical data reveal the influence of Madrid on the geochemistry of Manzanares' sediments, clearly manifested by a marked increase in the concentration of typically “urban” elements Ag, Cr, Cu, Pb and Zn, downstream of the intersection of the river with the city's perimeter. The highest concentrations of these elements appear to be associated with illegal or accidental dumping of waste materials, and with the uncontrolled incorporation of untreated urban runoff to the river. The natural matrix of the sediment is characterised by fairly constant concentrations of Ce, La and Y, whereas changes in the lithology intersected by the river cause corresponding variations in Ca–Mg and Al–Na contents. In the final stretch of the river, the presence of carbonate materials seems to exert a strong geochemical control on the amount of Zn and, to a lesser extent, Cu immobilised in the sediments. This fact suggests that a variable but significant proportion of both elements may be susceptible to reincorporation in the aqueous phase under realistic environmental conditions.

Doctoris Francisci Suarez ... de Societate Iesu ... Varia opuscula theologica ...

1. De concursu, motione, & auxilio Dei lib III - 2. De scientia Dei futurorum contingentium lib. II - 3. De auxilio efficaci brevis resolutio - 4. De libertate diuinae voluntatis relectio prior - 5. De reuiuiscentia meritorum relectio altera - 6. De iustitia Dei disputatio

Doctoris Francisci Suarez ... de Societate Iesu ... Varia opuscula theologica ...

Segundo imp. tomado del colofón en 3A8r