Relationships between polychlorinated biphenyls in molluscs, hydrological characteristics and human pressures, within Basque estuaries (northern Spain).

Interannual variability of polychlorinated biphenyls (PCBs), measured in the soft tissues of Mytilus galloprovincialis mussels and Crassostrea gigas oysters, collected from estuarine waters within the Basque Country (Bay of Biscay), are investigated. Samples were collected in the autumn, between 2002 and 2011. Sites located within the ports of Bilbao and Pasaia showed the highest PCBs concentrations in molluscs; the lowest were observed in the mouth of the Oka estuary, an area of low population and industrial activity. Congener profiles of PCBs in the tissues of molluscs reveal the predominance of hexachlorobiphenyls (CB153 and CB138). In addition, redundancy analysis has shown that residence time, river flow and a 'pressure index' explain 57% of the variability in the PCB congener concentrations (the higher the values of these variables, the higher the concentration). Finally, Σ7PCB median concentrations in molluscs and sediments, collected from nearby sampling sites, were found to be moderately correlated (r(2)=0.513, p<0.01).

Biomonitoring of metals under the water framework directive: detecting temporal trends and abrupt changes, in relation to the removal of pollution sources.

Temporal trends in metal concentrations, i.e. Ag, Cd, Cu, Cr, Hg, Ni, Pb and Zn, measured in soft tissues of Mytilus galloprovincialis mussels and Crassostrea gigas oysters collected from estuarine waters within the Basque Country (Bay of Biscay), have been investigated to determine if actions undertaken have improved the environmental quality of rivers and estuaries. Data compiled between 1990 and 2010 have been analysed statistically, applying the Mann-Kendall and the Mann-Whitney-Wilcoxon tests. Moreover, in those cases with significant trends, the Kolmogorov-Zurbenko Adaptive (KZA) filter was applied to detect abrupt changes. Results showed significant decreasing trends for some metals, i.e. Ni, Cu, Pb and Zn, and differences between medians. Trend lines showed abrupt changes occurring between 1998 and 2002. Therefore, observed downward trends were related to increased wastewater treatment and diversions of discharges to ocean, implemented mainly during 2000-2002.

Dissolved metal background levels in marine waters, for the assessment of the physico-chemical status, within the European Water Framework Directive.

The European Water Framework Directive (WFD) has, as its ultimate aim, a reduction in the concentrations of hazardous substances in the marine environment, i.e. 'background' values. Hence, the determination of natural background levels of heavy metals, to distinguish between natural element concentrations and anthropogenically-influenced concentrations, is highly relevant. Some studies have shown the convenience in the derivation of local background levels, especially if they are necessary for environmental assessment. Nevertheless, although such studies exist for sediments, there are only a few previous investigations on metal background values in sea water. Likewise, there is not any standard procedure to determine such levels in waters, nor general agreement on the statistical methodologies to be applied. In this contribution, background levels of heavy metals (As, Cu, Mn, Ni, Pb and Zn), in estuarine and coastal waters within the Basque Country (northern Spain), according to ranges in salinity, are estimated using statistical tools. Ni and Pb have been considered elsewhere (2455/2001/EC) as priority substances under the WFD. Hence, this approach can assist further in the determination of water reference conditions, to assess chemical and physico-chemical status in other European countries; this, affects, ultimately, the ecological status, as defined within the WFD.

Maximum likelihood mixture estimation to determine metal background values in estuarine and coastal sediments within the European Water Framework Directive.

Some of the recently derived European Directives, such as the Water Framework and Marine Strategy, have, as ultimate aims, to achieve concentrations of hazardous substances in the marine environment near background values. Hence, the determination of natural background levels, in marine sediments, is highly relevant. The present study proposes the use of the maximum likelihood mixture estimation (MLME) to determine regional background levels and upper threshold of metal concentration, with the Basque Country as a case study (with a data set of 575 samples, from estuarine and littoral areas, including both intertidal and subtidal sediments). The heuristic procedure is applied with unimodal data distributions (Cd, Cr, Fe and Ni) and the mixture density estimations, based upon maximum likelihood, are carried out with polypopulational data distributions (As, Cu, Mn, Hg, Pb and Zn). The upper limits of the distribution are proposed, as the limits between 'High Status' and 'Good Status' (according to the Water Framework Directive terminology). The regional upper limits were 0.45 microg g(-1) for Cd, 71 microg g(-1) for Cr, 53,542 microg g(-1) for Fe, 57 microg g(-1) for Ni, 24 microg g(-1) for As, 64 microg g(-1) for Cu, 447 microg g(-1) for Mn, 0.27 microg g(-1) for Hg, 66 microg g(-1) for Pb, and 248 microg g(-1) for Zn. The results from this study can assist further in the determination of sediment reference conditions, to assess chemical status, within the above-mentioned directives; likewise, it will be studied as a useful methodology in determining regional metal backgrounds in other European countries.