Large-scale spatial pollution patterns around the North Sea indicated by coastal bird eggs within an EcoQO programme.

To categorize the marine environmental health status, the Oslo and Paris commissions have recently formulated Ecological Quality Objectives (EcoQOs) for many ecological features including the contamination of coastal bird eggs with mercury and organochlorines. In this study, we describe spatial and temporal patterns of egg contamination around the North Sea and compared them to the EcoQOs. Concentrations of mercury, polychlorinated biphenyl (ΣPCB) congeners, dichlorodiphenyltrichloroethane (ΣDDT) and derivatives, hexachlorobenzene (HCB) and hexachlorocyclohexane (ΣHCH) isomers were analysed in two tern species (Sterna hirundo and Sterna paradisaea) and Oystercatcher (Haematopus ostralegus) eggs collected between 2008 and 2010 in a total of 21 sites in seven countries surrounding the North Sea. Hg, ΣPCB and HCB were highest in the southern sites, while ΣDDT and ΣHCH concentrations were greatest in eggs from the western North Sea and the Elbe estuary. There were rarely any consistent decreases over time for any compounds. In the terns, Hg, HCB and ΣHCH increased at most sites, ΣPCB and ΣDDT in Sweden and Norway. In the Oystercatcher, HCB and ΣHCH increased at more than the half of the sites, ΣPCB, ΣDDT and Hg at several German sites. In the terns, Hg, ΣPCB and ΣDDT exceeded the EcoQO in all, HCB in most years and sites. At most sites, ΣHCH fulfilled the EcoQO in some study years. In the Oystercatcher, Hg, ΣPCB and ΣDDT exceeded the EcoQO in all or most years and sites. HCB and ΣHCH fulfilled the EcoQO in some or all years at most sites. The EcoQO was exceeded most frequently in estuaries. We conclude that EcoQOs are suitable for drawing contamination patterns of the coastal North Sea in an easily understandable manner, offering the opportunity to harmonize the EcoQOs with coordinated environmental monitoring programmes.

Sample preparation method for the ER-CALUX bioassay screening of (xeno-)estrogenic activity in sediment extracts.

The application of bioassays to assess the occurrence of estrogenic compounds in the environment is increasing in both a scientific and statutory context. The availability of appropriate validated methods for sample pre-treatment and analysis is crucial for the successful implementation of bioassays. Here, we present a sample preparation method for the bioassay screening of estrogenic activity in sediment with the in vitro Estrogen Receptor mediated Chemical Activated LUciferase gene eXpression (ER-CALUX) assay. The method makes use of an Accelerated Solvent (ASE) or Soxhlet extraction with a mixture of dichloromethane and acetone (3:1, v/v), followed by clean up of the extract by Gel Permeation Chromatography (GPC). Recoveries of a panel of 17 pollutants differing largely in physical-chemical properties from spiked sediment were determined and appeared to be on average about 86%. Furthermore, the estrogenic potencies of all test compounds were individually assessed by determination of concentration-response relationships in the ER-CALUX assay. Concentration dependent estrogenic potency was found for 14 of the 17 compounds, with potencies of about 10(5) to 10(7) fold lower than the natural estrogenic hormone 17beta-estradiol. Anti-estrogenic potency was assessed by testing combinations of estradiol and individual test compounds, but was found for none of the compounds. The low estrogenic activity of the test compounds in the spiking mixture was well recovered during GPC treatment of the pure mixture, but did not contribute significantly to the background estrogenic activity present in the spiked sediment. Application of the method to field samples showed that estrogenic activity can be found at different types of locations, and demonstrated that levels between locations may vary considerably over relatively short distances.

MODELKEY. Models for assessing and forecasting the impact of environmental key pollutants on freshwater and marine ecosystems and biodiversity.

BACKGROUND: Triggered by the requirement of Water Framework Directive for a good ecological status for European river systems till 2015 and by still existing lacks in tools for cause identification of insufficient ecological status MODELKEY (http:// www.modelkey.org), an Integrated Project with 26 partners from 14 European countries, was started in 2005. MODELKEY is the acronym for 'Models for assessing and forecasting the impact of environmental key pollutants on freshwater and marine ecosystems and biodiversity'. The project is funded by the European Commission within the Sixth Framework Programme. OBJECTIVES: MODELKEY comprises a multidisciplinary approach aiming at developing interlinked tools for an enhanced understanding of cause-effect-relationships between insufficient ecological status and environmental pollution as causative factor and for the assessment and forecasting of the risks of key pollutants on fresh water and marine ecosystems at a river basin and adjacent marine environment scale. New modelling tools for risk assessment including generic exposure assessment models, mechanistic models of toxic effects in simplified food chains, integrated diagnostic effect models based on community patterns, predictive component effect models applying artificial neural networks and GIS-based analysis of integrated risk indexes will be developed and linked to a user-friendly decision support system for the prioritisation of risks, contamination sources and contaminated sites. APPROACH: Modelling will be closely interlinked with extensive laboratory and field investigations. Early warning strategies on the basis of sub-lethal effects in vitro and in vivo are provided and combined with fractionation and analytical tools for effect-directed analysis of key toxicants. Integrated assessment of exposure and effects on biofilms, invertebrate and fish communities linking chemical analysis in water, sediment and biota with in vitro, in vivo and community level effect analysis is designed to provide data and conceptual understanding for risk arising from key toxicants in aquatic ecosystems and will be used for verification of various modelling approaches. CONCLUSION AND PERSPECTIVE: The developed tools will be verified in case studies representing European key areas including Mediterranean, Western and Central European river basins. An end-user-directed decision support system will be provided for cost-effective tool selection and appropriate risk and site prioritisation.

A chemical and toxicological profile of Dutch North Sea surface sediments.

Chemical and toxicological profiles were assessed in surface sediments (fraction <63 microm) from the southern North Sea. In extracts of freeze-dried samples, polybrominated biphenyl (PBB), Irgarol 1051 and phthalate concentrations were below the respective detection limits (except di(2-ethylhexyl)phthalate, which was between 170 and 3300 microg kg(-1) dry weight (dw)). Hexabromocyclododecane (HBCD) concentrations were between 0.8 and 6.9 microg kg(-1)dw, with highest concentrations at river mouths. Polybrominated diphenylethers (PBDE) concentrations were 0.4-0.6 microg kg(-1)dw, decabromodiphenylether (BDE209) 1-32 microg kg(-1)dw. The ratio BDE209/PCB153 was used as a tracer for recent emissions, and pointed towards a BDE209 source in the Western Scheldt's upper estuary. PCBs and PAHs were between 0.19-4.7 and 2.6-200 microg kg(-1)dw respectively and generally had highest concentrations at near-shore locations and river mouths. Responses in the Microtox broad-spectrum and the Mutatox genotoxicity assays were generally low, with near-shore locations giving higher responses. The umu-C genotoxicity and the ER-CALUX assay for estrogenicity showed no response, with the exception of one near-shore location (IJmuiden outer harbour, ER-CALUX). Highest dioxin-like toxicity (DR-CALUX) was found at near-shore locations, in the outflow of the Rhine/Meuse estuary including a dumping site of harbour sludge. At the Oyster Grounds, DR-CALUX responses appeared to be linked to the occurrence of larger PAHs (4-6 rings). A new, non-destructive clean up procedure resulted in significantly higher DR-CALUX responses than the current protocol. The Dutch legislation on disposal of harbour sludge at sea, dictates the use of the conventional clean up procedure. Our results therefore indicate that probably more dioxin-like toxicity associated with harbour sludge is disposed off at sea than assumed.

Dissolved PCBs, PAHs, and HCB in pore waters and overlying waters of contaminated harbor sediments.

Aqueous concentrations of polychlorinated biphenyls (PCBs), polyaromatic hydrocarbons (PAHs), pentachlorobenzene, and hexachlorobenzene (HCB) were determined by exposing low-density polyethylene (LDPE) strips to the pore waters and the overlying water in two contaminated harbors. LDPE strips were also exposed in the laboratory to sediment slurries and to stagnant sediments collected at the same locations. Surprisingly short equilibration time scales (1-60 days for log K(ow) < 7) were observed for the exposures to sediment slurries. This was a result of a profound decrease in transport resistance, due to the presence of particles in the aqueous boundary layer. Concentrations in the pore water were calculated from the initial uptake rates and the dissipation rates of performance reference compounds. Good correspondence existed with concentrations estimated from the equilibrium amounts in the strips and LDPE-water partition coefficients. Sediment-water partition coefficients for PAHs were higher than for PCBs and chlorobenzenes by approximately 1 order of magnitude. A one-dimensional diffusion model was used to describe contaminant uptake by LDPE strips from stagnant sediments. The results indicated that 95% of the PAHs and 50% of the PCBs were immobile on a time scale of two months. A comparison of concentrations in pore waters and water columns indicated that a fair degree of equilibrium existed for PCBs and that one sediment was a potential source of PAHs. Concentrations of HCB near a former discharge site were higher by a factor of 6 compared to reference locations.