Rubén Villares

Seasonal variation and background levels of heavy metals in two green seaweeds

Seasonal variation in the contents of different metals (Al, Cr, Cu, Fe, Mn, Ni and Zn) in two genera of macroalgae, Ulva and Enteromorpha was studied at 22 sites on the northwest coast of Spain. The seasonal variation in the different metals followed a similar pattern in both seaweeds and appeared to be caused by dilution during the period of maximum growth and concentration during periods of slow growth. Fluvial inputs of Al, Fe and Mn in autumn and winter appeared to accentuate the latter effect: the concentrations of these three metals in both macroalgae and of Cr in Enteromorpha were highest at those sites most influenced by inputs from rivers. The background levels of Cr, Cu, Ni and Zn in the algae in summer and winter were established.

Ulva and Enteromorpha as indicators of heavy metal pollution

We studied the use of two genera of green macroalgae, Ulva and Enteromorpha, as indicators of heavy metal contamination on the northwest coast of Spain. We evaluated the extent of external contamination by fine particles adhering to the algal thallus and found that although not a problem in Ulva, it may be in Enteromorpha samples. The mean levels of metals in both seaweeds were in accordance with previously reported levels in different species of the genera in clean areas. A large number of significant correlations between levels of metals in macroalgae and in sediment (for both the total and labile fractions) were found. However, almost all of the coefficients of correlation decreased after geochemical normalization of sediment metal concentrations.

Background heavy metal levels in estuarine sediments and organisms in Galicia (northwest Spain) as determined by modal analysis

We investigated metal (Al, Fe, Mn, Co, Cr, Cu, Ni, Zn and Pb) concentrations in surface sediments (107 samples) and intertidal organisms (424 samples of macroalgae, phanerogams, molluscs and polychaetes) from 44 estuarine areas in Galicia (northwest Spain). Three acid extraction procedures (HCl, HNO3 and HNO3 + HF) were used. Following analysis of the effect of sediment particle size distribution on metal contents, Al content was selected as a normalization element. For most species and most metals, there was only minor contamination of the organism samples by particulate matter, confirming the efficiency of the washing and depuration procedures used and thus obviating the need to correct for such contamination on the basis of Fe contents. Background metal levels in the sediments and organisms were estimated by modal analysis. To the best of our knowledge, this is the first time that this method has been used for this purpose.

Heavy Metals in Sandy Sediments of the Rías Baixas (NW Spain)

We studied the concentrations of certain heavy metals in the total and labile fractions of sandy sediments from four embayments situated on the northwestern coast of Spain. In orderto compensate for the effects of the heterogeneity in texture ofthe different samples, data were normalized. Organic carbon was the most suitable normalizing factor for copper, lead and zinc inthe total fraction and copper in the labile fraction, and iron was the most suitable for the other metals in both fractions.Enrichment of copper, lead and zinc in these sediments may have been caused by sewage contamination. The percentages of extractability for chromiun were remarkable.

Use of macroalgae stored in an Environmental Specimen Bank for application of some European Framework Directives.

Different European Framework Directives have established a series of objectives for conservation of the coast, and monitoring tools must be made available to test compliance with these aims. In the present study the use of macroalgae deposited in an Environmental Specimen Bank was evaluated as a possible environmental tool for monitoring the coastal ecosystem. The concentrations of Al, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn in three species of the genus Fucus (Fucus spiralis, Fucus vesiculosus and Fucus ceranoides) were measured at sampling sites distributed along the coast of Galicia (NW Spain). In the period 1990-2001, the concentrations of the metals were higher in 1990 than in 2001, with the exception of: i) Mn in F. ceranoides and Fe in F. spiralis-F. vesiculosus, for which there were no differences between the sampling periods, and ii) Zn in F. vesiculosus and Fe in F. ceranoides, for which the concentrations were higher in 2001 than in 1990. In the period 2001-2007 concentrations of the metals were more stable, especially in F. ceranoides (e.g. Al, Fe, Hg, Ni and V). The concentrations were also more stable vin F. vesiculosus in 2005 (i.e. Al, Cr, Fe, Mn and Zn). The population density distributions are consistent with the results of the statistical tests. The results indicate that macroalgae of the genus Fucus may be useful for applying different European Framework Directives, given that the macroalgae are sufficiently sensitive to changes in concentrations of metals, and may be suitable for long-term monitoring and used for the detection of increased concentrations of metals (real-time monitoring).

Metal levels in estuarine macrophytes: Differences among species

With the aim of studying the interspectific differences in the bioaccumulation of a series of elements in six species of estuarine macrophytes, we measured the concentrations of various metals (Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn), as well as C and N, in several species of macroalgae and one species of seagrass in estuaries in northwest Spain. To facilitate the interpretation of the results, we also determined the concentrations of the same metals in sediments. Contamination by particulate metal did not appear to be important. The levels of Cu in the different species were generally high in comparison with those found in similar studies; in contrast, the concentrations of Pb and Zn were relatively low. The metal concentrations showed greater variability and a distibution that was further from normal than those of C and N. In general the highest concentrations of elements were found inEnteromorpha spp. andZostera noltii, and the lowest occurred inUlva spp. There were several significant positive correlations among tissue concentrations of Cr, Cu, and Ni. There were also significant correlations between tissue concentrations of N and Zn, suggesting possible synergetic effects between them. Cluster analysis clearly revealed that the chemical composition ofZ. noltii differed from that of the macroalage. Macroalgae were not grouped according to their taxonomic position, therefore it appears that the concentrations of the elements depended more on the ecological traits of the macroalgal species rather than on any possible, physiological differences among different taxonomic groups. Of the species studied,Ascophyllum nodosum andEnteromorpha spp. appeared to be the best biomonitors of metal contamination.

Seasonal variations in concentrations of macro- and micronutrients in three species of brown seaweed

Abstract We studied variations through 1 year in concentrations of several macronutrients (C, N, P, Na, K, Ca, Mg, S) and micronutrients (Fe, Mn, Cu, Zn) and water content in tissues of the brown seaweeds Ascophyllum nodosum, Fucus vesiculosus and Fucus spiralis at two sites in a coastal embayment in northwest Spain. The annual mean concentrations of the nutrients in A. nodosum were very similar at both sampling locations. There were no significant differences between sites in the concentrations of N, P, Na, K, Ca, S, Fe, Mn or Cu, the C:N or N:P ratios or in the water content, whereas the chemical composition of this species was notably different at the site where it coexisted with F. vesiculosus (the only parameters that were not significantly different were concentrations of Ca, Cu and the N:P ratio). The C:N:P ratios and the clear seasonal variability in N in all species, with minimum values in summer, suggest limitation by this element. Along with N, K was the only other element that varied throughout the seasons in all of the species, and this was most notable in F. vesiculosus. Minimum concentrations of K were also observed in summer, which might indicate limitation by this element. Seasonal variations in C were only observed in the Fucus species; they followed a reverse trend from those of N and K, as the highest levels occurred in summer. The highest concentrations of P and Zn in F. vesiculosus were also observed in spring. No obvious seasonal trends were observed in the remaining minerals.

Biomonitoring urban fluvial contamination on the basis of physiological stress induced in transplants of the aquatic moss Fontinalis antipyretica Hedw.

We examined the effects of urban-derived fluvial contamination on aquatic bryophytes with the aim of improving use of these organisms for active biomonitoring of this type of contamination. Samples of the aquatic moss Fontinalis antipyretica were transplanted to five sites of a river affected by different levels of urban contamination. The aquatic contamination was characterized by a series of physical and chemical parameters, which were then related to the physiological responses determined in transplants of the bryophyte. Comparison of the data revealed the physiological parameters that best differentiated between levels of contamination. The active biomonitoring technique proved to be a clear and rapid method of determining the existence of a contamination gradient on the basis of the degree of pigmentary and photosynthetic stress in the moss transplants. Of the parameters considered, the concentration of phaeopigments and the net photosynthetic rate provided the clearest responses.

Arsenic and Mercury in Native Aquatic Bryophytes: Differences Among Species

This study investigated the capacities of five species of aquatic bryophytes to accumulate As and Hg from their natural habitats in rivers in Galicia (NW Spain). The distributions of the concentrations of both elements in all species were skewed to the right, with a higher incidence of extreme values in the As data, which may indicate a greater degree of contamination by this metalloid. There were no significant differences in the accumulation of either of the elements between the different species studied, which justifies their combined use as biomonitors of As and Hg, at least in the study area.

Contribution of atmospheric deposition to tissue concentrations of mercury in aquatic bryophytes

In this biomonitoring study, we measured the temporal variations in concentrations of mercury in samples of aquatic bryophytes from rivers in a region that received large inputs of the metal via atmospheric deposition. In the first year of sampling, the presence of an important source of atmospheric deposition of Hg (a lignite-fired power plant) led, during the rainy season, to elevated concentrations of the metal in catchments situated downwind of the prevailing winds. High concentrations of the metal were even detected in samples from apparently clean rivers in isolated mountain sites within the downwind catchments. Substitution of the type of fuel (high quality imported carbon instead of brown coal) used in the power plant greatly reduced Hg emissions in subsequent years. Application of spatial interpolation techniques to dense monitoring networks with aquatic bryophytes, without taking into consideration the catchment borders, appears suitable for studying extensive atmospheric pollution derived from a large scale source of contamination. This study also demonstrates the importance of environmental specimen banks in retrospective studies of contamination, as they enable posterior analysis of contaminants that for various reasons cannot be analyzed at the time of sampling.