Peter Lepom

Levels and trends of polybrominated diphenylethers and other brominated flame retardants in wildlife.

In this paper, we review the available data for polybrominated diphenylethers (PBDEs) and other flame retardants in wildlife, with the exception of fishes from Europe and North America which are covered in more detail elsewhere. More data are available for PBDEs than for other compounds, and these show that some of these compounds have become widely distributed in the environment, being found in samples from Europe, Australia, Azerbaijan, North America and the Arctic. Most available data relate to birds and their eggs and marine mammals, but the results of two food web studies are also included. The detection of PBDEs in pelagic marine mammals which feed in deep offshore waters, including baleen whales, indicate that these compounds have found their way into deep-water, oceanic food webs as well as the coastal/shallow sea examples described in detail. In the North Sea study, the most marked increase in lipid-normalised concentrations of six BDE congeners occurred during transfer from predatory fish to marine mammals. In the St. Lawrence Estuary study, marked differences in the ratios observed between species suggested that some fish species may be able to metabolise BDE99.A number of time trend studies have also been conducted, notably in guillemot eggs from Sweden (1969-2000), beluga whales from the Canadian Arctic (1982-1997 and 1989-2001) and from the St. Lawrence Estuary (1988-1999), and ringed seals from the Canadian Arctic (1981-2000). In the temperate latitudes, from these and other studies (e.g. in dated sediment cores), PBDE concentrations began to rise earlier than in those from high latitudes, in line with data for production and use. These trends have now slowed in many cases. Declines could be expected in Europe for many congeners following the cessation of manufacture and use of the penta-mix formulation in the EU, though these are not yet apparent in environmental samples. In Arctic biota, however, the rapidly rising concentrations seen currently in Canada could be expected to continue for some time, reflecting continued production and use of the penta-mix formulation in North America (>95% of the world total) and the impact of long-range atmospheric transport.

Analysis and assessment of heavy metal pollution in suspended solids and sediments of the river Danube.

The Joint Danube Survey (JDS)--a comprehensive monitoring survey to assess the environmental pollution status of the river Danube--was carried out in 2001. Samples were taken at 74 positions along the river from Neu-Ulm (River-km 2589) down to the Danube Delta at the Black Sea (River-km 0) and in 24 main tributaries and anabranches. Besides other biological and chemical parameters, concentrations of Al, As, Cd, Cr, Cu, Fe, Pb, Mn, Hg, Ni, and Zn were determined in sediments and suspended solids. Lowest heavy metal concentrations were measured around River-km 1800. After an increase down to River-km 1000 (the Irongate Reservoir), a constant level or a slight decrease could be found down to and in the Danube Delta. Very high element concentrations were determined at only a few stations of the river Danube and in some tributaries. An evaluation of the pollution status of the river was carried out by enrichment factors (EFs) calculated using adapted background concentrations of heavy metals. Except single sampling sites and some tributaries, the pollution of the river Danube by As, Cr, Cu, Pb, Hg, Ni, and Zn can be regarded as rather low. However, elevated concentrations of Cd were found in both investigated matrices, particularly in the lower stretch of the river Danube beginning at the Irongate.

Common implementation strategy for the water framework directive (2000/60/EC)

This Technical Guidance Document on Biota Monitoring (the Implementation of EQSbiota) aims to facilitate the implementation of environmental quality standards (EQS) in biota under the Water Framework Directive by addressing in particular the sampling strategies appropriate for monitoring programmes designed to assess compliance with biota EQS. It is Guidance Document No. 32 in the series of guidance documents prepared to support the Common Implementation Strategy (CIS) for the Water Framework Directive. It elaborates extensively on the content of Guidance Document No. 25 on Chemical Monitoring in Sediment and Biota under the Water Framework Directive, and is complemented by Guidance Document No. 33, the Technical Guidance Document on Analytical Methods for Biota Monitoring. Guidance Documents 32 and 33 together address the requirement for guidance on biota monitoring mentioned in Article 3(8a) of Directive 2008/105/EC as amended by Directive 2013/39/EU. The original Directive 2008/105/EC included biota standards for mercury, hexachlorobenzene and hexachlorobutadiene. In Directive 2013/39/EU, biota EQS were introduced for three other existing priority substances (fluoranthene, polyaromatic hydrocarbons and brominated diphenylethers), and set for four new priority substances (dicofol, perfluorooctane sulfonic acid and its derivatives, hexabromocyclododecane, and heptachlor/heptachlor epoxide). This guidance document takes into account the fact that trend monitoring in sediment and/or biota is required for several other priority substances as specified in Article 3(6), and indicates how trend monitoring data can be used to check compliance with biota EQS, but does not elaborate on trend monitoring as such. This document constitutes guidance and Member States are therefore not legally required to follow the recommendations contained in it. Member States are, however, required to use methods compliant with the requirements of the Environmental Quality Standards Directive 2008/105/EC and the Quality Assurance/Quality Control Directive 2009/90/EC.

Xenoestrogens in the River Elbe and its tributaries.

4-Alkylphenols, 4-alkylphenol ethoxylates, 4-alkylphenoxy carboxylates, bisphenol A, bisphenol F, 4-hydroxyacetophenon, 4-hydroxybenzoic acid and steroid hormones were analyzed in water samples of the River Elbe and its tributaries Schwarze Elster, Mulde, Saale, Havel and Schwinge. Additionally, freshly deposited sediments (FDS, composite samples) of the River Elbe and its tributaries were analyzed. The concentrations in water samples ranged from (in ng/l): bisphenol A 4 to 92, branched nonylphenol 13 to 87, branched nonylphenol ethoxylates <0.5 to 120, 4-tert. nonylphenoxy carboxylates <10 to 940 and 4-hydroxybenzoic acid 4 to 12. Steroid hormones were only detected in the Czech tributaries Jizera and Vltava in concentrations near the limit of quantification. In FDS samples the concentrations amounted to (in g/kg d.w.): bisphenol A 10-380, branched nonylphenol 27-430, branched nonylphenol ethoxylates 24-3700, nonylphenoxy carboxylates <50 and 4-hydroxybenzoic acid 23-4400. Increased bisphenol A concentrations were found in water and FDS samples taken from the Czech-German border at Schmilka and the mouth of the Schwinge (only water sample). According to studies conducted in the Elbe Estuary and the German Bight, the River Elbe must be considered as a major source of pollution for the North Sea in respect of the compounds analyzed. A comparison of bisphenol A concentrations, 4-alkylphenols and the corresponding ethoxylates analyzed in the River Elbe and its tributaries with those found in other German surface waters indicated a low level of contamination. The evaluation of the data based on LOEC-values indicated that the concentrations were well below the effectivity threshold for some 4-alkylphenols. According to recent ecotoxicological investigations, for example, with prosobranch snails, bisphenol A concentrations found in water samples of the River Elbe and its tributaries may well be detrimental to aquatic organisms. On the basis of the monitoring data and its implications for estrogenic potency the inclusion of bisphenol A in the list of priority substances (European Union Directive 2000/60/EC, Annex X) should be considered.

Needs for reliable analytical methods for monitoring chemical pollutants in surface water under the European Water Framework Directive

The state of the art in monitoring chemical pollutants to assess water quality status according to Water Framework Directive (WFD) and the challenges associated with it have been reviewed. The article includes information on environmental quality standards (EQSs) proposed to protect the aquatic environment and humans against hazardous substances and the resulting monitoring requirements. Furthermore, minimum performance criteria for analytical methods and quality assurance issues have been discussed. The result of a survey of existing standard methods with a focus on European (EN) and international standards (ISO) for the analysis of chemical pollutants in water is reported and the applicability of those methods for the purpose of compliance checking with EQSs is examined. Approximately 75% of the 41 hazardous substances for which Europe-wide EQSs have been proposed can be reliably monitored in water with acceptable uncertainty when applying existing standardised methods. Monitoring in water encounters difficulties for some substances, e.g., short-chain chlorinated paraffins (SCCPs), polybrominated diphenyl ethers (PBDEs), tributyltin compounds, certain organochlorine pesticides and six-ring PAHs, mainly due to a lack of validated, sufficiently sensitive methods that are applicable in routine laboratory conditions. As WFD requires monitoring of unfiltered samples for organic contaminants more attention needs to be paid to the distribution of chemical pollutants between suspended particulate matter and the liquid phase. Methods allowing complete extraction of organic contaminants from whole water samples are required. From a quality assurance point of view, there is a need to organise interlaboratory comparisons specifically designed to the requirements of WFD (concentrations around EQSs, representative water samples) as well as field trials to compare sampling methodologies. Additional analytical challenges may arise when Member States have identified their river basin specific pollutants and after revision of the list of priority substances.

The Elbe flood in August 2002: Organic contaminants in sediment samples taken after the flood event

Abstract In the course of this study 37 sediment samples were analyzed. They were taken after the flooding in September 2002 along the Elbe and at the mouths of its major tributaries. The sampling program covered the entire river stretch that was affected by the floods, from Obristvi (Czech Republic) to the Elbe estuary (North Sea) on the German coast. Analyses were performed for dioxins, nonylphenols, nonylphenol ethoxylates, bisphenol A, DEHP, musk fragrances, polybrominated diphenylethers, chloroalkylphosphates, organochlorine compounds, PAH, and organotin compounds. The results show that only a few weeks after the flood, contaminant concentrations in solid matter were comparable to those prevailing beforehand. Significant sources of contaminant input proved to be the tributaries Vltava (Moldau), Bilina (both in the Czech Republic), and the Mulde (Germany), as well as industrial and municipal sewage treatment works (STW) located along the Elbe. Further point sources are to be found in still water zones such as harbors and abandoned channels. These sources are activated when erosive action stirs up older sediments. Statistical analyses of the congener distribution of the dioxins provided evidence on the sources of these contaminants and freight levels in different river sections. The chemical analyses were complemented by results of ecotoxicological investigations with two sediment organisms (Chironomus riparius and Potamopyrgus antipodarum).

Mercury levels and trends (1993–2009) in bream (Abramis brama L.) and zebra mussels (Dreissena polymorpha) from German surface waters

Mercury concentrations have been analysed in bream (Abramis brama L.) and zebra mussels (Dreissena polymorpha) collected at 17 freshwater sites in Germany from 1993-2009 and 1994-2009, respectively, within the German Environmental Specimen programme. Mercury concentrations in bream ranged from 21 to 881 ng g(-1) wet weight with lowest concentrations found at the reference site Lake Belau and highest in fish from the river Elbe and its tributaries. Statistical analysis revealed site-specific differences and significant decreasing temporal trends in mercury concentrations at most of the sampling sites. The decrease in mercury levels in bream was most pronounced in fish from the river Elbe and its tributary Mulde, while in fish from the river Saale mercury levels increased. Temporal trends seem to level off in recent years. Mercury concentrations in zebra mussels were much lower than those in bream according to their lower trophic position and varied by one order of magnitude from 4.1 to 42 ng g(-1) wet weight (33-336 ng g(-1) dry weight). For zebra mussels, trend analyses were performed for seven sampling sites at the rivers Saar and Elbe of which three showed significant downward trends. There was a significant correlation of the geometric mean concentrations in bream and zebra mussel over the entire study period at each sampling site (Pearsons correlation coefficient=0.892, p=0.00002). A comparison of the concentrations in bream with the environmental quality standard (EQS) of 20 ng g(-1) wet weight set for mercury in biota by the EU showed that not a single result was in compliance with this limit value, not even those from the reference site. Current mercury levels in bream from German rivers exceed the EQS by a factor 4.5-20. Thus, piscivorous top predators are still at risk of secondary poisoning by mercury exposure via the food chain. It was suggested focusing monitoring of mercury in forage fish (trophic level 3 or 4) for compliance checking with the EQS for biota and considering the age dependency of mercury concentrations in fish in the monitoring strategy.

Determination of hydrocarbons in water – interlaboratory method validation before routine monitoring

The clarification of hydrocarbon input into the Baltic sea via rivers is one of the priority issues of the 4th Pollution Load Compilation (PLC-4) within the framework of international Baltic Sea marine monitoring. An interlaboratory comparison was conducted to check the applicability of a new method for the determination of hydrocarbons by solvent extraction and gas chromatography. Surrogate oil solutions with known hydrocarbon content were distributed among the participants for preparation of water samples of different hydrocarbon concentration. In using these concentrations as assigned values and by setting target values for precision, the proficiency of participating laboratories could be tested as a qualifying step before involvement in PLC-4 routine monitoring. The results of the exercise indicate that hydrocarbons in water samples can be monitored as a mandatory test item within the framework of PLC-4.