Butyltin residues in blue mussels (Mytilus edulis) and arkshells (Scapharca broughtonii) collected from Korean coastal waters

Butyltin compounds (BTs) including tributyltin (TBT) and its degradation products, di- (DBT) and mono-butyltin (MBT), were determined in bivalves such as blue mussels (Mytilus edulis) and arkshells (Scapharca broughtonii) collected from Korean coastal waters. BTs were detected in all the blue mussels and arkshells analyzed. The concentrations of total butyltin (sigmaBTs: MBT + DBT + TBT) in blue mussels and arkshells ranged from 49 to 2500 ng/g and 29 to 87 ng/g wet weight, respectively. Higher concentrations of BTs were found in blue mussels collected from Okpo and Kohyonsong Bays and Jangsengpo Harbor where large shipyards and harbors are located with dry-dock facilities. This suggested that maritime activities nearby the harbors play a major role as the source of BTs. Concentrations of TBT in mussels collected from Korea were one of the highest values reported, suggesting ongoing TBT contamination in Korea. Among BTs, TBT was the predominant compound both in blue mussels and arkshells collected from almost all the sampling locations, indicating the fresh input of TBT in Korean coastal waters. Smaller mussels tended to accumulate BTs at higher concentrations than larger ones, which may be due to higher filtration rate of small mussels and/or contact with surface microlayer in intertidal zones.     

Butyltin compounds in sediment and fish from the Polish Coast of the Baltic Sea

Concentrations of mono- (MBT), di- (DBT), and tri-(TBT) butyltin compounds were measured in eggs, liver, and muscle of nine species of fish from four regions of the Baltic Sea - the Firth of Vistula, the Gulf of Gdańsk, Puck Bay, and the mouth of the Vistula River. The overall concentration ranges among all the fish sampled from the four sites were: < 7 to 79 ng/g for MBT, 6 to 1100 ng/g for DBT, 7 to 3600 ng/g for TBT, and 16 to 4800 ng/g for total BTs, on a wet wt basis. The highest concentration of total BTs was found in herring liver from the Firth of Vistula (4800 ng/g, wet wt) and in roach muscle from Puck Bay (3300 ng/g, wet wt), while the least concentration was found in burbot eggs and liver from the Vistula River (39 and 32 ng/g, wet wt, respectively). TBT was the major form of BTs present in most samples analyzed. Sediment samples collected from shipyards in the Gulf of Gdańsk contained butyltin concentrations ranging from 1.2 to 46 μg/g (dry wt) for MBT, 2.0 to 42 μg/g for DBT, and 2.6 to 40 μg/g for TBT. As with the fish, the majority of the BTs in sediment were present as TBT, which suggested recent exposure of the aquatic environment of the region to TBT.     

Distribution of butyltin and derivatives in oyster shells and trapped sediments of two estuaries in Cantabria (Northern Spain)

Distribution of butyltin compounds (BTs) and derivatives (monobutyltin, MBT; dibutyltin, DBT and tributyltin, TBT) was analysed in Crassostrea gigas oyster shells and the sediments trapped in the shell chambers, from two different estuaries in Cantabria (Northern Spain), with very different environmental conditions, where previous data have not been reported. Inorganic tin analysis in oyster shells was performed in order to study the degradation of BTs. Shell thickening and losses in biological growth are related with the presence of TBT, and were determined using three morphological indexes. Total BTs concentrations, expressed as Sn, ranged from 18.0 ng g(-1) to 176.7 ng g(-1) in sediments, and from 2.4 ng g(-1) to 11.1 ng g(-1) in oyster shells. Total inorganic tin concentrations ranged from 1775.0 ng g(-1) to 4781.3 ng g(-1) in oyster shells. The amount of BTs in oyster shells has been associated with the concentrations in the sediments trapped in the shell chambers. Partition coefficients between oyster sediments and oyster shells show the affinity of BTs by the sediments and the higher inorganic tin in oyster shells does not seem to be related to the BTs pollution.     

The recovery of populations of dogwhelks suffering from imposex in the Firth of Forth 1987-1997/98

The impact of tributyltin (TBT) contamination on dogwhelk (Nucella lapillus) populations was assessed at 33 sites in the Firth of Forth, UK, during spring 1997 and summer 1998. The sex ratio of the animals; the ratio of juveniles to adults; the degree of imposex, as determined by the relative penis size index (RPSI); and the total tin concentration in a sample of dogwhelk tissue were used as measurements of TBT impact on dogwhelk populations. These data were compared with data from a similar survey carried out at the same sites in the Firth of Forth in 1987 (Bailey, S.K., Davies, I.M., 1988. Tributyltin contamination in the Firth of Forth (1975-1987). Science of the Total Environment 76, 185-192.) before restrictions were introduced on the use of TBT. The results demonstrate a general recovery in dogwhelk populations from the impact of TBT at the majority of the sites studied, although at six of the sites, the RPSI value remains high enough to suggest breeding problems in the population. It is suggested that large vessels are responsible for localised cases of imposex within the Firth of Forth.     

Butyltin residues in livers of humans and wild terrestrial mammals and in plastic products

Butyltin compounds (BTs) including mono-(MBT), di-(DBT) and tributyltin (TBT) were determined in livers of humans and wild terrestrial mammals, such as raccoon dogs (Nyctereutes procyonoids) and monkeys (Macaca fuscata) from Japan. In addition, 22 samples of plastic products were analyzed. BT residues were detected in all the liver samples of humans and raccoon dogs, with concentrations of <360 ng/g wet wt, whereas concentrations in the liver of monkeys were either less than the detection limit or were only in trace levels. Elevated concentrations of BTs, particularly DBT (<140,000 ng/g) and MBT (<130,000 ng/g), were found in some plastic products, such as baking parchments made from siliconized paper and gloves made up from polyurethane. The results of a cooking test using the above baking parchment indicated the transfer of BTs to foodstuffs. These observations suggest expansion of BT contamination among terrestrial mammals. BT pollution from industrial appliances, such as plastic stabilizers and catalysts other than those of marine origin as antifouling agents, are suggested as alternative sources of exposure.     

Trace elements and butyltins in a Dall's porpoise (Phocoenoides dalli) from the Sanriku coast of Japan

Concentrations and body burdens of 14 trace elements (Hg, Cr, Mn, Co, Cu, Zn, Sr, Ag, Cd, V, Se, Pb, Mo, and Fe) and butyltins (BTs) (tributyltin TBT, dibutyltin DBT, and monobutyltin MBT) were determined in various tissues of a mature male Dall's porpoise (Phocoenoides dalli) collected off the Sanriku coast of Japan. Selective accumulation in this porpoise was observed for Hg, Mn, Cu, Ag, Mo, Fe, and total BTs (TBT, DBT, and MBT) in the liver, Cd in the kidney, Zn, Sr, V, Pb, and Co in the bone, and Se in the skin. In contrast, Cr concentrations in all tissues were similar. This distribution pattern in this mature porpoise was in general agreement with the accumulation characteristics of trace elements and butyltins reported for other marine mammals. The whole body of the porpoise contained approximately 62 g Fe, 8.8 g Zn, 4.0 g Sr, 0.6g Se, 0.41 g Cu, 0.19 g Hg, 0.17 g Cd, 0.16 g Mn, 0.05 g Cr, 0.009 g Ag, 0.008 g Mo, 0.005 g Pb, 0.004 g Co, and 0.7 mg of BTs (0.4 mg TBT, 0.2 mg DBT, and 0.1 mg MBT). Metabolism of TBT to its breakdown products of this porpoise seems to be limited, since TBT still accounted for about half of the total burden of BTs. As in the cases of Hg, Mn, Cu, Se, and Fe, the muscle was the most important reservoir (43%) for the whole body burden of total BTs, 80% of which was TBT, and thus muscle played a crucial role in the higher body composition of TBT in this Dall's porpoise.     

Contamination of butyltin compounds in Malaysian marine environments

Concentration of butyltin compounds (BTs), including tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) and total tin (SigmaSn) were determined in green mussel (Perna viridis), 10 species of muscle fish and sediment from coastal waters of Malaysia. BTs were detected in all these samples ranging from 3.6 to 900 ng/g wet wt., 3.6 to 210 ng/g wet wt., and 18 to 1400 ng/g dry wt. for mussels, fish and sediments, respectively. The concentrations of BTs in several locations of this study were comparable with the reported values from some developed countries and highest among Asian developing nations. Considerable concentration of BTs in several locations might have ecotoxicological consequences and may cause concern to human health. The parent compound TBT was found to be highest than those of its degradation compounds, DBT and MBT, suggesting recent input of TBT to the Malaysian marine environment. Significant positive correlation (Spearman rank correlation: r2=0.82, P<0.0001) was found between BTs and SigmaSn, implying considerable anthropogenic input of butyltin compounds to total tin contamination levels. Enormous boating activities may be a major source of BTs in this country, although aquaculture activities may not be ignored.     

Evaluation of mitogen-induced responses in marine mammal and human lymphocytes by in-vitro exposure of butyltins and non-ortho coplanar PCBs

The effects of exposure to butyltin compounds (BTs: tributyltin; TBT, dibutyltin; DBT and monobutyltin; MBT) and non-ortho coplanar PCBs (IUPAC 77, 126 and 169) on marine mammals and human lymphocyte were evaluated. Peripheral blood mononuclear cells (PBMCs) isolated from Dall's porpoises (Phocoenoides dalli), bottlenose dolphins (Tursiops truncatus), a California sealion (Zalophus californianus), a larga seal (Phocoa largha) and humans (Homo sapiens) were exposed at varying concentrations of BTs and coplanar PCBs. Concanavalin A (Con A)-stimulated mitogenesis found significantly suppressed (P<0.01) when the cells were exposed at 300 nM (89 ng/ml) of TBT and 330 nM of DBT (77 ng/ml), while MBT showed little cytotoxicity at treatment levels of up to 3,600 nM (620 ng/ml). BTs concentrations in the liver of Dall's porpoises from Japanese coastal waters ranged between 81-450 ng/g for TBT and 200-1,100 ng/g (wet wt.) for DBTs, which is greater than the cytotoxic levels registered in this study. In contrast, non-ortho coplanar PCBs did not suppress cell proliferation at concentrations of up to 30 nM (10 ng/ml). The residue levels of coplanar PCBs in the blubber of Dall's porpoises were 0.12-1.3 ng/g, which were one order of lower than those levels that do cell proliferation. When cells were exposed to a mixture of TBT/DBTand coplanar PCBs, the proliferation was significantly reduced to 33 nM DBT plus 34 nM CB-77 and 33 nM DBT plus 28 nM CB-169 mixtures, respectively. The investigations relating the contaminant-induced immunosuppression in marine mammals have been focused on persistent organochlorines such as PCBs. pesticides and dioxin compounds. However, this study suggested the possibility of BTs could also pose a serious threat to the immune functions in free-ranging marine mammals and humans.     

Global pollution monitoring of butyltin compounds using skipjack tuna as a bioindicator

Butyltin compounds (BTs) including mono- (MBT), di- (DBT), tri-butyltin (TBT) and total tin (sigmaSn), were determined in the liver of skipjack tuna (Katsuwonus pelamis) collected from Asian offshore waters (off-Japan, the Japan Sea, off-Taiwan, the East China Sea, the South China Sea, off-Philippines, off-Indonesia, the Bay of Bengal), off-Seychelles, off-Brazil and open seas (the North Pacific). BTs were detected in all the skipjack tuna collected, suggesting widespread contamination of BTs even in offshore waters and open seas on a global scale. Considering specific accumulation, Sex-, body length- differences and migration of skipjack tuna did not seem to affect BT concentrations, indicating rapid reflection of the pollution levels in seawater where and when they were collected. Skipjack tuna is a suitable bioindicator for monitoring the global distribution of BTs in offshore waters and open seas. High concentrations of BTs were observed in skipjack tuna from offshore waters around Japan, a highly developed and industrialized region (up to 400 ng/g wet weight). Moreover skipjack tuna collected from offshore waters around Asian developing countries also revealed the levels comparable to those in Japan (up to 270 ng/g wet weight) which may be due to the recent improvement in economic status in Asian developing countries. High percentages (almost 90%) of BTs in total tin (sigmaSn: sum of inorganic tin+organic tin) were found in the liver of skipjack tuna from offshore waters around Asian developing countries. This finding suggests that the anthropogenic BTs represent the major source of Sn accumulation in skipjack tuna from these regions.     

Survey of organotin compounds in rivers and coastal environments in Portugal 1999-2000

In the period from April 1999 to May 2000, organotin pollution, namely butyl and phenyltins, was investigated in coastal and continental waters (46 stations), estuarine sediments (15 stations) and mussels (Mytilus galloprovincialis) (13 stations) throughout Portugal. Sampling points were chosen in areas of specific industrial, agricultural and harbor activities. Butyltins (BTs) were the only tin species identified of which tributyltin (TBT) was found in the whole area. Concentrations of TBT in river water ranged from 3 to 30 ng L(-1) (as Sn), marine sediment ranged from 4 to 12 microg kg(-1) (as Sn), whereas concentrations in mussel tissue ranged from 2.5 to 490 microg kg(-1) (as Sn). Given that some water samples appeared to be contaminated by higher monobutyltin (MBT) and dibutyltin (DBT) concentrations, the role of biological degradation and direct inputs from agricultural and industrial applications areas are discussed. The study compares depleted butyltin pollution in sediments and mussels of the Portuguese coastline associated with antifouling paints with previously reported levels. Inputs in river waters are more related to (i) PVC leaching and (ii) industrial sources, in some cases discharged by municipal wastewaters.     

Assessment of tin and butyltin species in estuarine superficial sediments from Gipuzkoa,Spain

Ten superficial sediments from river estuaries of Gipuzkoa (North Spain) were collected and analyzed for nine metals (including tin, Sn) and butyltin compounds (monobutyltin, MBT; dibutyltin, DBT; tributyltin, TBT). Total metal concentration in the fine fraction (<63 micrometer) of the sediment was determined in aqua regia--hydrofluoric acid extracts by atomic absorption spectrometry. The butyltin species (BTs) were firstly extracted from the sediments with hydrochloric acid-methanol mixture. After derivatization with sodium tetraethyl borate, the organotin compounds were extracted by solid phase microextraction (SPME) in headspace mode. A fiber coated with 100 micrometer poly(dimethylsiloxane) was used for SPME. The organotin species were analyzed by gas chromatography-flame ionization detection. Analysis of the certified reference sediment (PACS-2) shown the suitability of the procedures for determination of metal contents and DBT-TBT species in contaminated sediments. Factorial analysis was used to examine the main sources of metals. Three factors represented more than 89% of the total variance of the metal system, and the Sn was related with Cu-Zn-Pb suggesting the same pollution source. The BTs concentrations in the area were high (TBT ranged from 0.05 to 5.48 mg Sn kg(-1)). The percentage of total butyltin species ( summation operator BTs) respect to the total Sn amount was higher than 4% in all the sediments, showing in the Bidasoa river estuary a remarkable value higher than 20%. Hence, the studied estuarine sediments reflect a pollution that is related with historical industrial and fishing activities of the area.     

The stability of butyltin compounds in a dredged heavily-contaminated sediment

A treatment process for marine sediment heavily contaminated with tributyltin (TBT) was designed that included dehydrating, sunlight drying and dumping processes. The time course in butyltin (BTs) compounds, TBT, dibutyltin (DBT) and monobutyltin concentrations were investigated in the sediment treated under various conditions (light (UV, sunlight and light exclusion), moisture (air-drying and water saturation) and wetting and drying cycles). Significant changes in all the BT compound concentrations with time were not found regardless of the sediment conditions for light and moisture. The results indicated the high stabilities of TBT and DBT in the sediments versus light and moisture condition changes, probably taking place in the treatment process. It is also estimated that the BTs in the sediment are resistant to photo-degradation and biochemical degradation and their half lives are relatively long. In contrast, the decreases in the TBT and DBT were observed during the wetting and drying cycle treatment for the water saturated sediment both during exposure to sunlight and under a dark condition. This result suggested the hypothesis that the TBT degradation could be accelerated by the high microbial activity induced by the moisture changing treatments.     

Sources and fate of butyltins in the St. Lawrence Estuary ecosystem

Butyltins (BTs) were determined in sediment, zooplankton, benthic fish and invertebrates in the St. Lawrence Estuary and its mixing zone with the Gulf of St. Lawrence (Canada) in an attempt to assess sources and fate of these compounds in a large ecosystem before the enforcement of the world-wide ban of TBT-based antifouling paints. All BTs (MBT, DBT and TBT) were found along the studied area (450 km) where the traffic of large vessels occurs around the year. Concentrations of total butyltins (BTs) in surface sediment were below 6 ng Sn g(-1) d.w. Total BTs concentrations found in zooplankton samples at the mouth of the Saguenay Fjord were the highest (793 ng Sn g(-1) d.w.), indicating the influence of the Fjord on the St. Lawrence contamination. Although a relatively low contamination level was measured in sediment, total BTs concentrations ranged from 9 to 489 ng Sn g(-1) d.w. for benthic organisms. Biota-sediment accumulation factors (BSAFs), calculated on the basis of the organic carbon content in the sediment (concentrations normalized to 1% Corg), ranged from 0.9 to 98.3, and are an indicator of an important source of BTs from the Saguenay Fjord particulate matter. This may be explained by the fact that when TBT is released in a large and deep well stratified coastal environment, it could bind to the suspended particulate matter and then be taken in charge by water column organisms and may be mostly metabolised before it reaches bottom sediment. Sediment is not considered as the main contributor to the contamination of fish and invertebrates. It is expected that any reduction of direct inputs of TBT from ship hulls in a near future should result in a rapid reduction of butyltins in the St. Lawrence ecosystem.     

Seasonal variation in the composition and concentration of butyltin compounds in marine fish of Taiwan

For the first time, strong evidence is presented to demonstrate that the accumulations of butyltin compounds (BTs) exhibit seasonal variations with respect to their compositions and concentrations in marine fishes. Measurements were made on the benthic ponyfish Leiogenathus splendens and lizardfish Trachinocephalus myops inhabiting the west coast of Taiwan. In the whole body samples of the ponyfish, BT concentrations ranged from 236 to 2501 ng/g wet wt, with those in winter considerably higher than in the other seasons (p < 0.05 ). In a similar vein, proportions of mono- (MBT), di- (DBT) and tributyltin (TBT) differed significantly (p < 0.001) depending upon the season, with TBT (75 and 50%) dominant in winter and spring and DBT (37 and 57%) and MBT (42 and 24%) dominant in summer and autumn, respectively. In the lizardfish, the concentrations of BTs were one to two orders of magnitude higher in the liver than in the muscle, i.e. 3058-11,473 vs. 36-159 ng/g wet wt, respectively. Concentrations of MBT, DBT and TBT in the muscle ranged, respectively, from 5 to 14, 8 to 35 and 23 to 110 ng/g wet wt, with the major compound being TBT (57-69%) in all seasons. However, in the liver, DBT concentrations, ranging from 992 to 7797 ng/g wet wt, differed seasonally with a descending order of autumn>summer>spring (p < 0.05). Meanwhile, TBT (41%) was predominant in spring, whereas DBT (50 and 68%) was most heavily concentrated in summer and autumn (p < 0.001). Seasonally mediated physiological changes, such as dilution due to growth and metabolic compensation, may play important roles in forming different BT accumulation patterns among seasons and organisms.     

Concentrations of organotin compounds in sediment and clams collected from coastal areas in Vietnam

Levels of butyltin (BT) and phenyltin (PT) compounds were determined in sediments and clam Meretrix spp. collected from north and central coastal areas in Vietnam. Concentrations of TBT in sediments ranged from 0.89 to 34 ng g(-1) dry wt and those in clams ranged from 1.4 to 56 ng g(-1) wet wt. The levels of TBT in sediments and clams from Vietnam were within limits reported from other countries. Further, the TBT level in clams was lower than the tolerable average residue level (TARL) estimated based on tolerable daily intake (TDI). Trace amounts of PTs were also found in both sediment and clam samples. In sediments from north and central Vietnam, the concentrations of TBT were highest in the order of Hue (28 ng g(-1) dry wt), Cua Luc (15 ng g(-1) dry wt), Sam Son (6.3 ng g(-1) dry wt), and Tra Co (5.5 ng g(-1) dry wt). Among the clams from north and central Vietnam, the levels of TBT in clams from Cua Luc were dramatically high at 47 ng g(-1) wet wt. TBT formed the principal butyltin species in sediment at all sites studied. The ratios of TBT in sediment were higher among BT compounds at all study sites. Of total BTs, TBT was the dominant species in clams from almost all sites studied. In spatial distribution, TPT showed a pattern similar to TBT, suggesting the use of TPT as an antifouling paint. The partition coefficient between sediment and calms was calculated. The partition coefficients of TBT and TPT were 2.01 (0.56-5.5) and 9.23 (3.1-20), respectively. These results show that sediment-bound TBT is a source of contamination to clams in addition to dissolved TBT.     

The use of Littorina littorea for tributyltin (TBT) effect monitoring - Results from the German TBT survey 1994/1995 and laboratory experiments

Field investigations and laboratory experiments were performed to test the applicability of the intersex phenomenon in Littorina littorea for biological TBT-effect monitoring and to give further insights into toxicological aspects of intersex development. The intensity of the phenomenon is correlated with the degree of TBT contamination in the environment. Statistically highly significant correlations of biological indices and TBT concentrations in tissue and sediment exist. Intersex can be induced only in juvenile and sexually immature females and its intensity depends on the ontogenetic stage of development during TBT exposure. For the first time, malformations in male periwinkles closely related to the TBT contamination can be described; the reduction of male mamilliform penial glands shows highly significant correlations to TBT concentrations in tissues. The intersex phenomenon in Littorina littorea is proposed for a biological TBT-effect monitoring in those areas where the dogwhelk Nucella lapillus, as the more sensitive species in European surveys, is absent. The intersex index (ISI) as the mean value of the intersex stages in a sample should be used as the most sensitive biological parameter for the assessment of the TBT contamination in Littorina littorea.     

Organotins and imposex in the rock shell, Thais clavigera, from oyster mariculture areas in Taiwan

The amounts of organotin compounds such as butyltins [sigma BTs: tributyl- (TBT), dibutyl- (DBT), monobutyl- (MBT)] and phenyltins [sigma PhTs: triphenyl- (TPhT), diphenyl- (DPhT) and monophenyl- (MPhT)] in rock shells, Thais clavigera, from the northern (Shiangsan), central (Lukang) and southern (Chiku) Taiwan oyster mariculture areas varied with season and location. High values of sigma BTs (mainly TBT) and low values of sigma PhTs (mainly TPhT) were found during winter (January 1999) at Shiangsan, while high amounts of sigma PhTs (mainly TPhT) and low sigma BTs (mainly TBT) were found during summer (August 1998) at Lukang. The snails were also affected by imposex. Imposex at Shiangsan, Lukang and Chiku increased from 67.1, 59.3 and 36.7% in summer to 100, 100 and 80% in winter, respectively. Relative penis size indices similar trend at Chiku site. No male displayed rock shells were found at Shiangsan and Lukang in winter. Linear correlations between pseudopenis length versus TBT (r = 0.7655, P < 0.001), DBT (r = 0.4253, P < 0.05), MBT (r = 0.5865, P < 0.01) and TPhT (r = -0.6160, P < 0.01) were obtained significant. Among 200 samples, significant positive correlations between length (pseudopenis/shell) ratio of female versus TBT (r = 0.6944, P < 0.005) and sigma BTs (r = 0.6413, r < 0.01) were also observed. The weak correlations between length (pseudopenis/shell) ratio of female versus DBT (r = 0.3085) and MBT (r = 0.4240, P < 0.1) and TPhT (-0.4917, P < 0.05; negative correlation) could indicate that DBT, MBT and TPhT have little or no effect on the development of imposex in rock shells.     

Quantification of organotin compounds and determination of imposex in populations of dogwhelks (Nucella lapillus) from Norway

Unintentional effects of the antifouling agent tributyltin (TBT) have been discovered in marine gastropods as the induction of male sex characters in females, known as imposex. The occurrence of imposex in dogwhelks (Nucella lapillus) was investigated in 41 populations sampled in 1993-1995 along the Norwegian coast. A method for quantification of organotin species using gas chromatography and atomic emission detection (GC-AED) was developed. Some degree of imposex occurred in almost all populations of dogwhelks studied, except in four from Northern Norway. The concentration of organotin compounds in the gastropods from the unaffected populations was below the detection limit (7 ng Sn/g d.w.). The concentration of TBT in dogwhelks from affected populations was in the range 48-1096 ng Sn/g d.w. A positive relation between the concentration of TBT in dogwhelks and the degree of imposex was found.     

Accumulation of organotin in Littorina littorea and Mya arenaria from Danish coastal waters

Organotin concentrations were determined in seawater, sediment and selected molluscs collected from the vicinity of the island of Fyn, Denmark. The extent of organotin contamination varied with the proximity of sampling sites to marinas and commercial shipping activities. Seasonal reductions in environmental TBT concentrations coincided with removal of pleasure craft from marinas during the winter season. At marina sites, concentration factors for TBT were 150-1500 for sediment and 500-10,000 for Littorina littorea (compared with seawater concentrations). Away from marina sites, Mya arenaria concentrated TBT by a factor of 57,000 to 220,000. The concentrations of TBT in M. arenaria from relatively clean sites were more than 10 times higher than found in L. littorea from heavily polluted marinas. M. arenaria were absent from marina sites and their immediate surroundings. Of the total organotin found in M. arenaria throughout the year, 80-90% was in the form of TBT. In contrast, in L. littorea approximately 60-70% of the total organotin was present as TBT in spring, but this proportion fell to 20-40% during autumn and winter. M. arenaria shows potential as a bioindicator organism of TBT pollution as it appears to have a very limited ability to metabolise and eliminate TBT, yet can tolerate quite high levels of TBT exposure. L. littorea might be used as a bioindicator of short-term fluctuations in TBT concentrations at heavily polluted sites. It is concluded that continued presence of TBT in the Danish coastal ecosystem may still pose an ecotoxicological threat.     

Survey of butyltin contamination in Portuguese coastal environments

Butyltin compounds (MBT, DBT and TBT) in intertidal sediments collected in four different Portuguese coastal environments have been measured in order to evaluate the extent of contamination. The sites chosen were the Rias of Aveiro and Faro, and the Sado and Tejo estuaries. These zones were traditional areas for shellfish production in the recent past, but the effects of industrial development have caused a deterioration of the environment. Specific contaminations were derived from the harbour (commercial and/or fisheries) and shipyard activities, resulting in a release of TBT and causing the oyster populations of the above mentioned estuaries to almost disappear. Results presented in this study give a survey of TBT contamination levels found in the four areas. The paper discusses the importance of the pollution in comparison with other European coastal areas.