Belén Rubio

Geochemistry of Major and Trace Elements in Sediments of the Ria de Vigo (NW Spain): an Assessment of Metal Pollution☆

Ria de Vigo is a funnel-shaped, fault-bounded coastal embayment in Galicia, NW Spain. There are a number of important centres of population and industrial activity along its margins, which serve as sources of pollution. Sixty-six subtidal sediment samples have been collected in the Ria. The samples have been subjected to a total digestion technique and analysed for major and trace elements (Al, Fe,Ti, Mn, Cu, Pb, Cr, Zn, Co, As, Ni, Cd and Sr). Variations of absolute metal concentrations reflected variations in textural and/or carbonate and organic matter content. Geoaccumulation indexes and enrichment factors have been calculated to assess whether the concentrations observed represent background or contaminated levels. It is proved that the choice of the background plays an important role in the interpretation of the geochemical data. PCA was a very useful tool to define background values for metals in the Ria de Vigo area. These values were similar to regional values given by other authors. It is concluded that the Ria is slightly to moderately polluted for some of the studied metals. The spatial extent of pollution was examined, and it was found that the most polluted area is located in the inner and southern parts of the Ria.

Assessment of the health quality of Ria de Aveiro (Portugal): Heavy metals and benthic foraminifera

This work analyses the distribution of heavy metals in the sediments of Ria de Aveiro (Portugal) assessed by total digestion and sequential chemical extraction of the sediments. The influence of environmental parameters on the living benthic foraminiferal assemblages was studied. The most polluted parts in the Ria de Aveiro are areas where the residence time is high and cohesive sediments are deposited. Organic matter, which is an excellent scavenger for a number of metals, is in general more abundant in the finer deposits of this lagoon, which act as sinks of anthropogenic pollutants. This condition is observed in Aveiro canals and Murtosa channel where sediments with the highest concentrations of Zn, Pb, Cu, and Cr are found. The sediments of Murtosa channel are also enriched in As, Co and Hg. In Aveiro canals the enrichment of heavy metals is mostly related to the past industrial production at their margins (ceramic and metallurgy), whereas in Murtosa channel with effluent discharges of the Chemical Complex of Estarreja. Foraminiferal density and diversity reach higher values near the lagoon mouth under higher marine influence and decline in general under very low-oxygen conditions. Some species seems to be indifferent to the increasing of TOC (e.g. Haynesina germanica and Ammonia tepida) and some have an opportunistic behaviour in areas with very depressed levels of oxygen (e.g. A. tepida and Quinqueloculina seminulum) whereas other species can better tolerate sulphide/reducing conditions (e.g. H. germanica, Bolivina ordinaria, Buliminella elegantissima, Bulimina elongata/gibba and Nonionella stella) a widespread condition in this lagoon. Foraminiferal density and some species are negatively correlated with concentrations of heavy metals. A most sensitive group of species to higher concentrations of heavy metals is identified (such as B. ordinaria, B. pseudoplicata and B. elongata/gibba) and another one of more tolerant species (such as H. germanica A. tepida and Q. seminulum). Foraminifera are more tolerate higher available concentrations (AC) of Zn in any phase than higher AC of Cu adsorbed do clay minerals (F1) and associated with Fe and Mn oxides (F2) and of Pb in F2; the phase F2, probably the most mobile phase, and even phase F1 seems to be more toxic than the increasing of metals in organic matter (F3).

Isotopic identification of natural vs. anthropogenic lead sources in marine sediments from the inner Ría de Vigo (NW Spain)

San Simón Bay, the inner part of the Ría de Vigo (NW Spain), an area previously identified as highly polluted by Pb, was selected for the application of Pb stable isotope ratios as a fingerprinting tool in subtidal and intertidal sediment cores. Lead isotopic ratios were determined by inductively coupled plasma mass spectrometry on extracts from bulk samples after total acid digestion. Depth-wise profiles of (206)Pb/(207)Pb, (206)Pb/(204)Pb, (207)Pb/(204)Pb, (208)Pb/(204)Pb and (208)Pb/(207)Pb ratios showed, in general, an upward decrease for both intertidal and subtidal sediments as a consequence of the anthropogenic activities over the last century, or centuries. Waste channel samples from a nearby ceramic factory showed characteristic Pb stable isotope ratios different from those typical of coal and petrol. Natural isotope ratios from non-polluted samples were established for the study area, differentiating sediments from granitic or schist-gneiss sources. A binary mixing model employed on the polluted samples allowed estimating the anthropogenic inputs to the bay. These inputs represented between 25 and 98% of Pb inputs in intertidal samples, and 9-84% in subtidal samples, their contributions varying with time. Anthropogenic sources were apportioned according to a three-source model. Coal combustion-related emissions were the main anthropogenic source Pb to the bay (60-70%) before the establishment of the ceramic factory in the area (in the 1970s) which has since constituted the main source (95-100%), followed by petrol-related emissions. The Pb inputs history for the intertidal area was determined for the 20th century, and, for the subtidal area, the 19th and 20th centuries.

Redox status and heavy metal risk in intertidal sediments in NW Spain as inferred from the degrees of pyritization of iron and trace elements.

Mariculture is an important economic activity in shallow marine areas of the Rías Baixas (Galicia, NW Spain). The maintenance of high product quality requires surveillance of environmental quality, including the risk of metal toxicity. In this study the redox status of intertidal sediments in the Bay of San Simón, and the risk of toxicity posed by their As, Cd, Cr, Cu, Mn, Ni, Pb and Zn contents, were evaluated by determination of operationally defined reactive, silicate-bound, organic and pyrite-related fractions of these elements and of Fe. The large silicate-bound fractions of most of these metals indicate their lithogenic origin; the main exception is Pb, which in all respects exhibits singular behaviour associated with its predominantly anthropogenic origin in a ceramics factory. In sediments with larger fine-grained particle contents, which are oxic only in the top few centimetres, greater proportions of the trace elements are present as sulphides or associated with sulphide minerals: the degree of pyritization of Fe (DOP) is 46% overall, and the pyrite fraction of some elements doubtless increases at the expense of the reactive fraction, most overall degrees of trace metal pyritization (DTMPs) lying in the range 10-50%. A decline in pyrite genesis at depths below about 18 cm in these sediments is attributed to the exhaustion of organic matter susceptible to metabolization by sulphide-generating bacteria. In coarse-grained, oxic sediments the oxidation of sulphides makes pyrite-related fractions very small, and reactive and silicate-bound fractions are negatively correlated; reactive fractions associated with Fe-Mn oxyhydroxides are large, and DOP and DTMPs are low (generally much lower than in mud-rich sediments), except for Pb. Most of the elements studied are mainly present in forms that are neither bioavailable nor potentially bioavailable, and so do not constitute a significant environmental threat. However, the high DTMPs of Cu and Pb indicate significant potential bioavailability, which should be taken into account in evaluations of environmental quality and the risk to bivalve cultures.

The degree of trace metal pyritization in subtidal sediments of a mariculture area: application to the assessment of toxic risk.

Four 2-3m sediment cores were taken at the sites on the periphery of mussel raft concentrations in the subtidal zone of the inner Ría de Vigo (Galicia, NW Spain) with a view to evaluate the potential risk to mariculture from sediment-borne trace elements (As, Cd, Cr, Cu, Mn, Ni, Pb and Zn). The distribution of each of these elements in reactive, organic, pyrite and silicate-bound fractions was determined at 64 samples, and these data were used to calculate the degree of trace metal pyritization (DTMP) of each metal/metalloid. In the top 10-20 cm, relatively oxic conditions led to As, Cd, Cu, Pb and Zn having large reactive fractions due to their association with Fe and Mn oxyhydroxides. At lower levels, anoxic conditions favoured by intense diagenesis led to the precipitation of trace metals and metalloids as sulphides, with or without association with pyrite. Particularly large pyrite fractions in the 20-100 cm layer are attributed to the organic matter of this layer being more marine in origin than that of deeper sediments. DTMP was greatest for Cu and As, and least for Pb, Zn and Cr. The risk of trace element toxicity in the event of disturbances instituting oxic conditions in these sediments is discussed.

The influence of weather and climate on the reliability of magnetic properties of tree leaves as proxies for air pollution monitoring

Monthly monitoring of magnetic properties of Platanus hispanica tree leaves was used to assess atmospheric pollution in Madrid (Spain) and its suburban town of Pozuelo de Alarcón. Magnetic susceptibility, isothermal remanent magnetisation and metal concentrations were analysed to study the sources of atmospheric pollutants and their spatial and temporal evolution. In addition to urban dust, our results indicated that lithogenic dust and incorporation of trace metals in the leaf tissue also control the magnetic susceptibility of tree leaves. Global comparisons with cities of different climatic regimes suggest that air humidity is the key factor controlling the relative influence of pollutants, lithogenic dust and biological effects on the magnetic properties of tree leaves. Interaction of the atmosphere and tree leaves depends not only on local meteorology but also on climate. Climate, especially air humidity, and meteorology need to be considered when interpreting the magnetic properties of tree leaves as an atmospheric pollution tool.

Diagenesis and anthropogenesis of metals in the recent Holocene sedimentary record of the Ría de Vigo (NW Spain)

To contribute to establishing a historical baseline for future evaluations of the environmental quality of the Ría de Vigo (NW Spain), we report metal contents determined in eight gravity cores obtained at representative locations in 1990 - before the installation of any wastewater treatment plants - and in fractions thereof that were obtained by the BCR sequential extraction method. The results suggest that early diagenesis had been influenced by both hydrodynamic conditions and organic matter input (the latter especially in areas devoted to mariculture), and that anthropogenic inputs had also affected the concentrations and between-fraction distribution of Cu, Pb, Zn and other metals in surficial sediments.

Propiedades magnéticas de los sedimentos de tipo estuarino. El caso de las Rías Baixas.

Este trabajo establece la utilidad de la susceptibilidad magnetica como indicador de la influencia marina y evolucion diagenetica en sedimentos costeros de las Rias Baixas. Para ello se investigo la variabilidad geografica de la susceptibilidad en 200 muestras de sedimentos marinos superficiales en las Rias de Vigo y Pontevedra. Su variabilidad vertical se estudio en 80 muestras de tres testigos de entre 60 y 90 cm de longitud extraidos en la Ria de Pontevedra. La susceptibilidad de las muestras superficiales aumenta progresivamente hacia mar abierto, y a medida que nos alejamos de las zonas de mayor influencia continental, estando relacionada con la textura y composicion del sedimento, y por tanto, con su procedencia. Los testigos, mas homogeneos litologicamente, mostraron una disminucion muy importante de la susceptibilidad con la profundidad, estando esta asociada a la evolucion diagenetica del sedimento. Para estudiar mejor estos procesos, se determino la composicion elemental y mineralogica, y ademas se midieron otras propiedades magneticas de muestras representativas. Estos resultados se analizaron conjuntamente con los datos sedimentologicos disponibles, lo que permitio establecer que la variabilidad de 151 D. Rey et al. Propiedades magneticas de los sedimentos de tipo estuarino... la susceptibilidad dependia de tres factores principales: (a) procedencia y origen de los sedimentos, (b) regimen hidrodinamico de la zona y (c) presencia de particulas contaminantes discretas de origen antropogenico. Tambien puede concluirse que la evolucion de las fases magnetomineralogicas durante la diagenesis temprana esta controlada por el contenido en materia organica, lo que a su vez determina el potencial de oxidacion-reduccion.

Low-level gamma spectrometry for pollution assessment in San Simón Bay (Vigo, Spain)*

A gamma spectrometer with HPGe detector of 50% relative efficiency and 1 cps total background has been dedicated to the measurement of an intertidal sediment core from a coastal environment at the Ria de Vigo (Spain). The area is affected by lead pollution and the source identification needs of a precise dating of the sediment core. Such a precise dating requires the measurement not only of the radionuclides directly involved in time calculation, as 210 Pb and 226 Ra, but also of ancillary radionuclides which inform about the dating model to apply and about the validity of its time estimation. Gamma spectrometry with Ge detectors performs a simultaneous measurement of the full content in γ-emitters of the sample. However, its use is limited by its high spectral background. We present the characteristics of our low- level background gamma spectrometer and also of Galea, the computing tool for the expert analysis of natural radionuclides. Both make possible to get the proper experimental results to reach a suitable dating. The results allowed us to detect a change in the sedimentation dynamics in the area under study, to verify the impact of lead pollution in the 210 Pb level, to obtain a sedimentation rate by using the CF:CS model with a suitable correction factor and, finally, to validate the sediment dating.

The ITRAX core scanner, a useful tool to distinguish anthropic vs. climatic influences in lagoon of Aveiro (N Portugal)

ABSTRACT Martins, V. A., Dias, J. A., Bernardes, C., Rubio, B., Bernabeu, A., , Rey, D., Soares, A.M., Sobrinho, F., Laut, L.M., Frontalini, F., Terroso, D., Miranda, P., Fernández-Fernández. S., Rodrigues, M.A., Figueira, R., Sousa, S.M., Amaral, P. Mahiques, M. and Rocha, F., 2013. The ITRAX core scanner, an useful tool to distinguish anthropic vs climatic influences in lagoon of Aveiro (N Portugal). The main goal of this work is to distinguish anthropic and climatic influences in sediments from the lagoon of Aveiro (Portugal). This study is based on a core (240-cm long) collected in Murtosa Channel. Optical and X-radiographic images and high-resolution elemental profiles were acquired with ITRAX micro-X-ray fluorescence (XRF) core scanner. Samples collected at each ≈3 cm along the core were analysed for grain size and total organic carbon. Furthermore, the fine fraction of selected layers was subjected to geochemical analysis by ICP-MS, after total acid digestion of the sediments, and mineralogical analysis, by XRD techniques. A radiocarbon age was determined by AMS, using molluscs shells collected at a depth of 90 cm. Sediments along the core are composed by fine and medium sand, with several mud layers. Sediments composing the first 100-cm may have been deposited after 1950, as it is indicated by the radiocarbon data, the increasing trend of Zn/Al, Pb/Al and Cu/Al and total concentrations of Zn, Pb, Cu, V, Cr, As and Ni in this interval that therefore might be linked with industrial activities of Chemical Complex of Estarreja. The progressive increase of Si/Al, Cl/Al, Rb/Al, K/Al and Br/Al and reduced Al concentrations, from the base to the top of this core, are interpreted as being related to higher marine influence and greater differences in tidal currents with longer exposition to air of the sediments with the consequent formation of brines favouring minerals precipitation in the area (e.g. anhydrite). These results seem to be a consequence of several works developed over time like: i) dredging to improve the navigation access to the harbour, located in the external sector of the lagoon; ii) the control of the course of some rivers influencing the supply of sediments. The tendency of sea level rise may have also emphasized the gradual increase of marine influence in this area. Fine-grained sections, related to an increase in Al, phyllosilicates, organic matter, pyrite and siderite contents would be attributed to phases of greater supply of fine-sediments during heavy rainfall events by the nearby Antuã river and other streams during negative phases of North Atlantic Oscillation. Higher deposition of organic matter enhanced diagenetic changes with pyrite and siderite formation. In the bottom of the core another record of pollution was unveiled to mining activities at the beginning of 20th century.