Michael J. Waldock

Antifouling Paint Booster Biocide Contamination in UK Marine Sediments

The proposed International Maritime Organization (IMO) ban on tributyltin (TBT) as an antifouling paint biocide, will raise the inevitability of the increased use of alternative paints containing copper and organic booster biocides. Although the fate of TBT in marine sediments has been extensively studied, very little work has been performed to assess the accumulation of organic booster biocides in sediments. A survey was conducted to determine concentrations of TBT, Irgarol 1051, the Irgarol 1051 metabolite GS26575 (2-(tert-butylamino)-4-amino-6-(methylthio)-1,3,5-triazine; also referred to as M1) and diuron in coastal and off-shore sediments. TBT was consistently determined at the highest concentrations and was detected in all sediments collected from Southampton Water, UK, along with the TBT degradation product dibutyltin (DBT). Irgarol 1051 was detected (0.01-0.11 μg/g) in some sediments collected from marinas, where high concentrations of these compounds have been measured in surface waters. The Irgarol 1051 metabolite 2-methylthio-4-tert-butylamino-6-amino-s-triazine (M1/GS26575) was only detected at a few locations at concentrations <0.001 μg/g, although higher concentrations were determined in surface waters (13-99 ng ng l). Diuron, thought to be present in the form of antifouling paint particles, was determined at a concentration of 1.4 μg/g in an enclosed marina. All analytes were found to be below the limit of detection in the sediments collected off-shore. The potential accumulation in sediments of the other two booster biocides currently used in the UK, zinc pyrithione and dichlofluanid, are also discussed

SURVEYS OF PLASMA VITELLOGENIN AND INTERSEX IN MALE FLOUNDER (PLATICHTHYS FLESUS ) AS MEASURES OF ENDOCRINE DISRUPTION BY ESTROGENIC CONTAMINATION IN UNITED KINGDOM ESTUARIES: TEMPORAL TRENDS, 1996 TO 2001

Plasma vitellogenin (VTG) concentrations and the presence of the ovo-testis (intersex) condition have been recorded in male flounder (Platichthys flesus) captured from several United Kingdom (UK) estuaries since 1996 as part of the endocrine disruption in the Marine Environment (EDMAR) project and earlier programs. It has been confirmed that plasma VTG concentrations in male flounder have remained elevated in several UK estuaries (e.g., Tees, Mersey, and Tyne) throughout the period covered by this study. However, the time-series data indicate that plasma VTG, a measure of environmental estrogen contamination, has decreased in fish captured from several estuaries, especially those of the Tyne and Mersey. Shorter time-series data sets from the Forth and Clyde estuaries also suggest a decrease in estrogen contamination at these sites. Trends associated with specific point sources of estrogenic contamination show site-specific patterns. For instance, plasma VTG levels in male flounder captured near the Howdon sewage treatment outfall (Tyne) have shown a steady decline to near baseline levels in 2001, while the plasma of male fish captured at a site adjacent to the Dabholm Gut discharge in the Tees estuary have shown little evidence of a sustained decline. The occurrence of the intersex condition was detected at a low but consistent prevalence through the study period, with the majority of cases recorded in fish captured from the Tyne and Mersey estuaries. The data set does not allow conclusions to be drawn about any temporal trends associated with this condition. The significance of the findings and possible mitigating influences are discussed in terms of the impacts on wild fish and the role of effluent treatment in reducing these.

Effects of paint-derived tributyltin on structure of estuarine nematode assemblages in experimental microcosms

A microcosm experiment was designed to evaluate the effects of different levels of paint-derived tributyltin (TBT), and different modes of exposure, on the diversity, feeding mode and assemblage structure of estuarine nematodes. Estuarine meiofauna were exposed to two types of treatments (mixture and deposit), containing uncontaminated sediment and sediment spiked with paint-derived TBT at 1 and 10 mg kg−1 for a duration of 4 and 8 weeks. In the mixture treatments, meiofauna assemblages were incubated in clean and contaminated sediments. In the deposit treatments meiofauna assemblages were exposed to the deposition of clean and contaminated sediments simulating the disposal of TBT-contaminated dredged material at sea. Effects of TBT on nematode species are likely to occur by (a) the uptake of leached TBT from the sediment pore water through their permeable cuticle, resulting in decreased diversity and increased changes in assemblage structure with increasing levels of TBT contamination, and (b) direct ingestion of paint-particles with food, resulting in a significant decline of nonselective deposit feeders in contaminated sediments. The numbers of many species differed greatly between mixture and deposit treatments. Results from multivariate analyses showed an immediate and dominant effect of burial on most nematode species in the deposit treatments compared to the longer-term effect of TBT contamination. The survival rates of nematode species in the top layer of these sediments depended on their ability to withstand TBT contamination as well as their potential to migrate, survive and reproduce in the deposit. This study unambiguously showed that the response of nematode species depended not only on the level of TBT contamination but also on the duration and mode of exposure to contaminated sediment, which should be taken into account when assessing the effects of TBT on aquatic communities.

Toxicity Characterization of Organic Contaminants in Industrialized UK Estuaries and Coastal Waters

This report describes the isolation and identification of organic toxicants present in marine surface waters collected from industrially impacted areas around the UK in 1997. The characterization process utilized Toxicity Identification Evaluation (TIE) procedures that have been adapted for marine samples and a small volume bioassay using the marine copepod Tisbe battagliai. The dissolved organic content of bulk water samples was isolated using a layered solid phase extraction system to provide sample concentrates which were tested for acute toxicity. Where acute toxicity was demonstrated, the extracts were fractionated using reverse phase HPLC and tested further. Each fraction showing toxicity was then analysed by gas chromatography-mass spectrometry. The results of this investigation demonstrate that surface water concentrates collected from several impacted estuaries show acute toxicity. Organic extracts from surface waters may be concentrated using simple chromatographic techniques to induce toxicity in test species. Fractionation showed that the majority of this toxicity is associated with low to medium polarity contaminants. Compounds that were identified by gas chromatography–mass spectrometry as the possible cause of toxic effect include alkylphenols, alkyl substituted naphthalenes, alkyl-substituted fluorenes and dimethyl benzoquinone, however, the identity of certain toxic compounds remains unknown. It is concluded that the technique is a valuable tool in identifying compounds that may be potentially harmful to the aquatic environment.