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.     

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.     

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.     

Three decades of tributyltin in the coastal environment with emphasis on Arcachon Bay, France

This account briefly reviews the fate, bioconcentration and effects of tributyltin (TBT) three decades after its introduction into the coastal environment. Data on TBT-related events that occurred in Arcachon Bay (gastropod imposex, oyster recruitment failure, oyster shell malformations, concentrations in water and sediments) are revised and reinterpreted. Historically, TBT concentrations in the waters of the open bay seldom exceeded 1 ng Sn l(-1) in the 1960s, likely surpassed the range of 100 ng Sn l(-1) from 1977 to 1981 (years when no oyster spat were collected and the local shellfish industry collapsed), and decreased to about 1 ng Sn l(-1) in the late 1980s and early 1990s following legislation in January 1982 banning TBT use. TBT pollution is discussed in relation to the green tides that have developed in Arcachon Bay since 1982.     

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.     

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.     

Horizontal distribution of butyltins in surface sediments from an enclosed bay system, Korea

Tributyltin (TBT), dibutyltin (DBT), and monobutyltin (MBT) compounds were quantitatively determined from surface sediment samples (total 59 stations) covering a whole basin where harbors, shipyards, and aquaculture farms were located. Butyltin compounds were detected from all the stations covering 640 km(2) of an enclosed bay system. TBT concentrations ranged from 4 to 382 ng/g as tin on a dry weight basis, and total butyltin concentrations, from 27 to 1763 ng/g. Horizontal distribution of TBT concentration showed apparent negative gradients from harbors and shipyards, indicating that its contamination was closely related to boating and dry-docking activities. However, TBT concentrations were decreased steeply from source areas. Elevated DBT and MBT levels in creeks imply the possible input of DBT from industrial wastewater. Total butyltin concentrations in sediments are significantly correlated with particulate organic carbon concentration for the subset of stations that are distant from source areas.     

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.     

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.     

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.     

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.     

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.     

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.     

Butyltins in water, biofilm, animals and sediments of the west coast of India

Biofilm, fish, oyster, mussel, clam, surface seawater, suspended particulate matter (SPM), and sediment samples were collected from marine and/or estuarine waters of the west coast of India. These samples were analysed for butyltin derivatives such as dibutyltin (DBT) and tributyltin (TBT). The concentrations DBT plus TBT varied between 2.4 and 8.3, 163 and 363 ng/l, 5 and 2853 ng/g dry wt in the SPM, seawater and sediment samples, respectively, of the Marmugao harbour. The values of DBT plus TBT ranged between 0.60 and 29, 123 and 242 ng/l and 1.4 and 65 ng/g dry wt in SPM, water and sediment samples, respectively, collected from the Mandovi estuary. In the Dona Paula Bay the DBT plus TBT varied from 10 to 89 ng/l in surface seawater, and TBT from 10 to 513 ng/g in biofilm samples. For the coastal sediment samples the concentration of DBT plus TBT ranged between 36 and 133 ng/g dry wt of sediment. For the animal samples the DBT plus TBT ranged between 58 and 825 ng/g dry wt of the tissue. Mussel tissues contained the highest amount of DBT plus TBT (825 ng/g dry wt tissue), whereas highest TBT concentration was recorded in the oyster (732 ng/g dry wt). TBT was generally the most abundant butyltin compound in most of the samples suggesting fresh inputs and/or less degradation of TBT. A wide range of the observed butyltin concentrations suggests the presence of localized areas of contamination. Leaching of tributyltin-containing antifouling paints from the ocean going ships, fishing and recreational boats, barges, and the inputs of TBT from the Goa shipyard and dry dock facility situated in the harbour are the probable sources of the DBT and TBT in the samples of the west coast of India. Higher levels of TBT were observed in biofilm relative to that in the surrounding seawater. When fed on TBT contaminated biofilm of the diatom Navicula subinflata, butyltin concentrations in the clam Paphia malabarica increased over the period of feeding suggesting the importance of biofilm in the transfer of butyltins to higher group of organisms.     

Organotin contamination in the Atlantic Ocean off the Iberian Peninsula in relation to shipping

Imposex in female snails, a bioindicator of TBT contamination, and the presence of organotins in snails' tissue and sediments were studied at nine sites off the western Iberian Peninsula. The study was part of a European project (acronym HIC-TBT) co-financed by the EU-LIFE programme, intending to investigate and communicate the impact of organotins from ships in marine ecosystems. Snails and sediments were sampled during two cruises in May/June 1999 and in January 2000 in areas of high, intermediate and low-shipping density. Imposex was found in female snails from several sampling sites, some of which had an imposex incidence of 100%. Differences in sensitivity were found between species; hence comparison of imposex levels between locations where different species were collected was not straightforward. Total organotin concentrations in sediments (sum of butyl and phenyltin compounds) ranged from 21 to 185 ng Sn g(-1) with higher values for most sites sampled in the vicinity of shipping lanes. Organotin concentration in snails' tissue ranged from <5 to 196 ng Sn g(-1), which are similar to those found in snails from other offshore areas contaminated by TBT. Overall, these results give further support to the recent ban on the use of organotin based antifouling paints to all ship size.     

Surface-sediment and hermit-crab contamination by butyltins in southeastern Atlantic estuaries after ban of TBT-based antifouling paints

Butyltin (BT) contamination was evaluated in hermit crabs from 25 estuaries and in sediments from 13 of these estuaries along about 2,000 km of the Brazilian coast. BT contamination in hermit crabs ranged from 2.22 to 1,746 ng Sn g^-1 of DBT and 1.32 to 318 ng Sn g^-1 of TBT. In sediment samples, the concentration also varied widely, from 25 to 1,304 ng Sn g^-1 of MBT, from 7 to 158 ng Sn g^-1 of DBT, and from 8 to 565 ng Sn g^-1 of TBT. BTs are still being found in surface sediments and biota of the estuaries after the international and Brazilian bans, showing heterogeneous distribution among and within estuaries. Although hermit crabs were previously tested as an indicator of recent BT contamination, the results indicate the presence of contamination, probably from resuspension of BTs from deeper water of the estuary.

Tributyltin in environmental samples from the Former Derecktor Shipyard, Coddington Cove, Newport RI

Tributyltin (TBT) was detected in all 24 surface sediment (top 2 cm) samples collected from Coddington Cove, Newport, RI. TBT surface sediment concentrations ranged from 32 to 372 ng Sn/g with a mean concentration of 146 ng Sn/g. Analyses of selected core sections detected TBT in at least the top 18 cm at all 7 stations where cores were collected. No consistent TBT concentration trends with depth for these cores suggest mixing is an important process in the sediment column. In one core (station 28), TBT was found in the 76-86 cm section at a concentration of 141 ng Sn/g; thus sediments are a significant sink for TBT. However, sediment mixing processes can enhance releases of bioavailable TBT. Mussels, clams and fish from Coddington Cove contain TBT at concentrations ranging from 9.2 to 977 ng Sn/g. TBT concentrations in lobsters were below the detection limit (<6 ng Sn/g). Based on available screening criteria, TBT concentrations in Coddington Cove sediment is likely to be having an adverse effect on the biota at some locations.     

Concentration of butyltin species in sediments associated with shipyard activity

Tributyltin (TBT) and dibutyltin (DBT) were analyzed in sediment samples collected from intertidal locations in Portland and Boothbay Harbor, Maine (USA) in 1990 and 1992. Surface sediment TBT concentrations ranged from 24 to 12 400 ng gm(-1) (dry wt basis). Sediments with the highest TBT concentrations were associated with shipyard hull washing/refinishing activities. Analysis of different layers in core samples found that butyltin concentrations decreased with depth at the Boothbay site and remained relatively constant with depth at the Portland site. Elutriate analysis showed that soluble TBT was released from a heavily contaminated sediment. The resulting TBT seawater concentration 1400 ng liter(-1) was < 0.03% of reported seawater solubilities of TBT and was only 0.14% of the total TBT in the sediment sample. This suggests that the TBT in the sediments analyzed is in a bound matrix form, such as paint particles, that releases the biocide slowly. The results indicate that there is a potential for future release of TBT from the resuspension of fine sediments at certain locations in Maine.     

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.     

Determination of butyltins in harbour sediment and water by aqueous phase ethylation GC-ICP-MS and hydride generation GC-AAS

Sediment and water samples have been collected between 1992 and 1995 for evaluating butyltin contamination in two marinas from the coastal area in The Netherlands, two years after the ban of TBT. Sediments extracts were analysed by capillary gas chromatography-inductively coupled plasma-mass spectrometry. Sediment concentrations for TBT showed no trend of decrease between 1992 and 1995 and were extremely high in the marina secluded from tidal action; 17.5 +/- 8.0 microg g(-1) and much lower for the marina with tidal action; 0.117 +/- 0.073 microg g(-1). High ratios between TBT and DBT in the sediments indicate that degradation mechanisms in the sediments are of minor importance. Dissolved butyltin compounds were analysed in water by means of gas chromatography-atomic absorption spectrometry. Water concentrations of TBT showed no clear trend of decrease between 1992 and 1995 and were high in the marina secluded from tidal action; 139 +/- 166 ng litre(-1) but much lower for the marina with tidal action; 48 +/- 98 ng litre(-1). An active degradation mechanism during summer periods was indicated by low (<1) TBT/DBT ratios in the water phase of the marina secluded from tidal action.