Long-term 2007-2013 monitoring of reproductive disturbance in the dun sentinel Assiminea grayana with regard to polymeric materials pollution at the coast of Lower Saxony, North Sea, Germany.

During biological effect monitoring studies of endocrine active compounds with the snail Assiminea grayana in 2007-2013, reproductive disorders including atresia, transformation of capsule/albumen glands into prostates in females and ovotestis, transformation of prostates to capsule/albumen glands, disruption of spermatogenesis, and calcification of tubules in males, were encountered in several years. The search of sources of endocrine active substances was first directed to antifouling biocides from paint particles and extended to leaching compounds from polymeric materials. In contrast to the reference sites, most of the observed disorders occurred at a station near harbors and dockyards polluted with residues from antifouling paints and polymeric materials. Beside of investigations about the potential ingestion of polymer particles by the snails, further investigations of compounds of polymeric materials with endocrine potential should follow.

Pathology and mass mortality of Pacific oysters, Crassostrea gigas (Thunberg), in 2005 at the East Frisian coast, Germany.

In 2005, Pacific oysters, Crassostrea gigas, were collected from May to September along the East Frisian coast and processed for histology. Because of mass mortalities in September, additional samples of moribund oysters and apparently healthy blue mussels, Mytilus edulis, were subjected to virological and ultrastructural investigation. The oysters displayed a variety of pathological conditions including viral gametocytic hypertrophy which is reported here for the first time from the German coast. Haemocyte aggregations in the digestive tract, in the intestinal mucosa and submucosa, in the mid-gut gland and in the ventricle of the heart were commonly observed at some stations. In association with mass mortalities, severe gill necrosis occurred which may have contributed to the high mortality rates. Total mortality rates of up to approximately 60% were seen. All size classes and thus age classes of oysters were affected, with highest mortality rates within the youngest age classes which had just reached sexual maturity (shell lengths <40 mm). The smallest dead oysters had shell lengths of 10 mm. The phenomenon was mainly restricted to C. gigas stocks in harbours, probably because of favourable conditions for infection, i.e. limited water exchange, less food availability, reduced oxygen content and higher pollution levels.

Some chemical contaminant of surface sediments at the Baltic Sea coastal region with special emphasis on androgenic and anti-androgenic compounds.

Androgenic and anti-androgenic compounds including p,p'-DDE, Diuron, Linuron, Fenarimol, Vinclozolin, 1-(3,4-dichlorophenyl) urea (DCPU), 1-(3,4-dichlorophenyl)-3-methylurea, (DCPMU), tributyltin (TBT) and triphenyltin (TPT) and their metabolites (DBT, MBT, DPT, MPT) as well as metallic elements (Ni, Cu, Zn, As, Cd, Pb, Co, Tl, Cr, Fe, Mn, Al, K, Mg, Na, Ca, Ba, Ti, Sn), PAHs (16 indicator compounds), DDTs and PCBs have been quantified in top layer (0-10 cm) of up to 37 surface sediment samples collected from several sites in costal zone of the Gulf of Gdansk, an inland freshwater area of Brdyujscie in Poland and the tidal flats of the Norderney Island, Wadden Sea in 2002-2003. These sites differed in the degree of anthropogenic activities, including chemical pollution and related impact on biota. Especially in sediments near shipyards, ship repair facilities, harbours, other industrial activities or close to municipal sewage treatment plant outlets butyltins, PAHs and some metallic elements were found at high concentrations. Diuron, Linuron and DCPMU were detected at a few sites, Fenarimol only once, while Vinclozolin and DCPU were not detected. DDT concentrations in the sediments from the Gdansk and Gdynia region of the Gulf show a stepwise decrease following the ban for production and use, while diffusion of PCBs at some industrial sites seems to continue. Elevated PAH concentrations in sediments seem to be mainly due to pyrogenic and less to mixed pyrogenic and petrogenic sources, while for a few sites rather petrogenic sources dominated. The reference sites in the Norderney Island, Wadden Sea showed similar or slightly higher loads of DDTs, BTs, PAHs, PCBs and metallic elements when compared to sediments from the least contaminated sites in the coastal Gulf of Gdansk area, while phenyltins were not detected at both spatially distant European areas.

Bioassays and selected chemical analysis of biocide-free antifouling coatings.

Over the years several types of biocide-free antifouling paints have entered the market. The prohibition of biocidal antifouling paints in special areas of some European countries such as Sweden, Denmark and Germany has favoured the introduction of these paints to the market. Several types of biocide-free antifouling paints were subjected to bioassays and selected chemical analysis of leachate and incorporated substances. Both non-eroding coatings (silicones, fibre coats, epoxies, polyurethane, polyvinyl) and eroding coatings (SPCs, ablative) were tested to exclude the presence of active biocides and dangerous compounds. The paints were subjected to the luminescent bacteria test and the cypris larvae settlement assay, the latter delivering information on toxicity as well as on efficacy. The following chemical analyses of selected compounds of dry-film were performed: The results of the bioassays indicated that none of the coatings analysed contained leachable biocides. Nevertheless, some products contained or leached dangerous compounds. The analyses revealed leaching of nonylphenol (up to 74.7 ng/cm2/d after 48 h) and bisphenol A (up to 2.77 ng/cm2/d after 24 h) from epoxy resins used as substitutes for antifouling paints. The heavy metal, zinc, was measured in dry paint film in quantities up to 576,000 ppm in erodable coatings, not incorporated as a biocide but to control the rate of erosion. Values for TBT in silicone elutriates were mostly below the detection limit of 0.005 mg/kg. Values for DBT ranged between <0.005 and 6.28 mg/kg, deriving from catalysts used as curing agents. Some biocide-free paints contained leachable, toxic and dangerous compounds in the dry film, some of which may act as substitutes for biocides or are incorporated as plasticizers or catalysts. Implications to environmental requirements and legislation are discussed.