厦门西港和闽江口表层沉积物中有机锡含量分布

对1996年10月在闽江口和1999年6月在厦门西港采集的表层沉积物样品中有机锡的含量进行分析,结果表明，TBT、DBT和MBT在所有厦门西港表层沉积物样品中均被检出，除XM21A和XM21B外，其它站位的TBT中Sn元素浓度均低于4.3×10     

Butyltin concentrations along the Japanese coast from 1997 to 1999 monitored by Caprella spp. (Crustacea: Amphipoda)

The concentrations of butyltins along the Japanese coastline were investigated from 1997 to 1999, 7 to 9 years after implementation of legislation limiting the use of tributyltin (TBT) in Japan. Seawater was sampled at 0.5 m depth, and Caprella spp. were collected from Sargassum spp. and aquaculture facilities from 18 areas within four broad areas along the coastline of Japan, i.e., the Pacific coast of northern Japan, the coast along the Sea of Japan, Tokyo Bay and adjacent areas, and western Japan. Butyltins (MBT, DBT and TBT) were detected in 32 of the 63 seawater samples with average concentrations of 4.6 ng MBT/l, 4.5 ng DBT/l and 6.8 ng TBT/l, respectively. Butyltin concentrations in seawater from western Japan indicate "hot spots" even in unpopulated areas. Butyltins (MBT, DBT and TBT) were detected in all samples of Caprella spp., varying from 2.3 ng BTs /g wet wt in C. penantis R-type from Tobishima Island in the Sea of Japan to 464 ng BTs /g wet wt in C. decipiens Mayer from Amakusa, western Kyushu. The BT concentrations in Caprella spp. form western Japan were significantly higher than those from other areas, including Tokyo Bay and adjacent areas, where large scale industry and international ports are located. These results indicate that butyltin contamination still remains even in unpopulated areas after the regulation on TBT usage, and that the regulation governing TBT usage since 1990 has not been effective enough to concede recovery of shallow water ecosystems around Japan.     

Fate of tributyltin in sewage sludge treatment

We have shown that municipal wastewater and sewage sludge are contaminated by organotins. Here, we investigate the behaviour and fate of tributyltin (TBT) in laboratory-scale sewage sludge treatment at various conditions including both aerobic and anaerobic, and mesophilic and thermophilic. Organotins were determined by capillary GC-FPD. Fresh raw sewage sludge was stored in a tank that was connected to five chemostats maintained at different conditions. Raw sludge contained TBT, dibutyltin (DBT) and monobutyltin (MBT) residues in the range of 0·28 to 0·83 mg/kg (dry weight). The volumetric TBT concentration was 10·5 μg/litre in the influent, and ranged from 7·4 to 8·3 μg/litre in the effluent of the different chemostats. In the anaerobic mesophilic treatment, concentrations of TBT did not decrease with increasing sludge residence time, DBT increased and MBT showed no clear trend. The DBT increase is suggested to be due to leaching from the PVC walls of the chemostats, and not to degradation of TBT alone. The TBT reduction did not show significant differences between the mesophilic and thermophilic anaerobic fermentors. These findings indicate that the degradation of TBT during sludge treatment is only low under all conditions tested.     

Bioaccumulation and toxicity of four dissolved metals in Paracentrotus lividus sea-urchin embryo

The bioaccumulation of four metals (Cd, Cu, Pb, Zn) dissolved in water was assessed measuring the concentrations recorded within sea-urchin larvae (Paracentrotus lividus, Lmk.) after a 48-h exposure period. Concurrently, the frequencies of abnormalities were evaluated at the 48-h pluteus stage to check the actual toxicity of such contaminants with regards to larval development. Maximum metal concentrations in the larvae reached 43.8 +/- 6.7 micrograms Cd g-1 dry weight (d.w.), 1269 +/- 392 micrograms Cu g-1 d.w., 3106 +/- 679 micrograms Pb g-1 d.w., 534 +/- 62 micrograms Zn g-1 d.w. Bioconcentration factors (BCFs) reached very high values for Pb (maximum value: 16,282 +/- 973) and indicated that the concentrations of Pb and Cd were directly related to the water concentration at least in the range of concentrations tested. Zn appeared to be partially regulated above a certain threshold concentration (between 5 and 25 micrograms l-1). Cu was accumulated with an active uptake at least below lethal threshold level (100 micrograms l-1). Nevertheless, above these thresholds, high mortality of embryos prevent any interpretation of Zn and Cu bioconcentration factors. Concurrent studies carried out on embryotoxicity confirmed the high toxicity of Cu towards sea-urchin pluteus larvae and highlighted the different behaviour of Cd. The internal Cd concentrations were directly related to the external ones, comparable to other non-essential metals, but Cd had little toxic effect on the initial larval development.     

Enzymatic activities in spermatozoa and butyltin concentrations in Baltic turbot (Scophthalmus maximus)

Spermatozoal enzymes of fish (NAD+- and NADP-dependent dehydrogenases and creatine kinase (CK)) were previously determined to be sensitive to tributyltin (TBT) in laboratory experiments and were thus indicated for use as biomarkers for TBT exposure. However, the potential ability of spermatozoal enzymes as biomarkers of TBT exposure has never been recapitulated in a field study. For this purpose, the kinetic activities of spermatozoal enzymes of the natural turbot Scophthalmus maximus population from the Gulf of Gdańsk (GDA) and the Pomeranian Bay (POM) in the southern Baltic Sea were measured. Gas chromatography/high-resolution mass spectrometry was used to determine the concentrations of TBT and its breakdown products, dibutyltin (DBT) and monobutyltin (MBT), in the muscle, liver and testes of the male turbot. Males from GDA had significantly higher enzymatic activities and butyltin (BT) content in tissues than those from POM. A general linear model (GLM) showed that lactate dehydrogenase (LDH), malate dehydrogenase (MDH), glucose-6-phosphate dehydrogenase (G6PDH) and CK activities increased significantly with BT concentration in the testes and liver. We indicate the potential effects of TBT pollution on the spermatozoal enzymes of Baltic turbot.     

Tributyltin compounds in mussels,oysters and sediments of Chinhae Bay,Korea

To study the historical and current status of the environmental levels of organotin compounds in Chinhae Bay in southeast Korea, mussels (Mytilus edulis galloprovincialis), oysters (Crassostrea gigas) and sediment cores were analysed for tributyltin (TBT) compounds. TBT concentrations were higher in oysters (mean: 0.25 μg TBT-Sn/g dry wt) than in mussels (mean: 0.20 μg TBT-Sn/g dry wt). The major sources of TBT are in the inner bay, and the highest TBT concentrations of 0.50 μg TBT-Sn/g (mussels) and 0.74 μg TBT-Sn/g (oysters) were observed at the site adjacent to the port. Concentrations of TBT decreased sharply with distance from the inner bay toward the outer bay and there was little TBT in the outer bay. A significant correlation was observed between this distance and the tissue TBT content of oysters and mussels. The concentration and percentages of TBT in sediment cores decreased with depth as a result of debutylation. Half-lives of TBT and dibutyltin (DBT) in sediments were 6.9 and 11.6 y, respectively. The TBT concentrations in mussels were higher than those in sediments by a factor of 4–7.     

Bioavailability and effects of sediment-bound TBT in deposit-feeding clams, Scrobicularia plana

Concentrations of tributyltin (TBT), dibutyltin (DBT), inorganic and total tin have been measured in water, sediments and deposit feeding clams, Scrobicularia plana, from 25 estuarine locations in England and Wales, in order to compare the bioavailability of different forms of the element. Abnormally high tin values in Scrobicularia from harbours and areas of high boating activity testify to the high bioaccumulation potential of organotins, notably TBT derived from anti-fouling paints, relative to inorganic tin.Infaunal deposit-feeding bivalves consistently contain higher concentrations of TBT than other benthic organisms indicating that sediments may be an important route for uptake. Significant correlations between sediment TBT values and residues in clams such as S. plana (r = 0·81, p < 0·001) support this hypothesis. Direct evidence of the bioaccumulation of sediment-bound TBT is provided from laboratory experiments in which Scrobicularia were exposed to TBT in water and in sediments, either separately or in combination. The results of these experiments clearly demonstrate a predominantly particulate component for TBT uptake in clams.The kinetics of TBT accumulation and elimination were studied in Scrobicularia exposed to sediments containing 0·3 and 1·0 μg/g TBT (as tin). Equilibrium concentrations in tissue are approached after 40 days.Sediments containing 10 μg/g TBT are acutely toxic to S. plana, although such concentrations are only likely to occur close to dockyards and large marinas. Preliminary laboratory and field observations suggest however, that clam populations could be affected at TBT concentrations in sediments of 0·3 μg/g and possibly lower.     

Imposex and organotin concentrations in Buccinum undatum and Neptunea antiqua from the North Sea: relationship to shipping density and hydrographical conditions

The presence and the development of imposex were investigated in the common whelk (Buccinum undatum) and the red whelk (Neptunea antiqua) from the open North Sea and the Skagerrak. Imposex development was related to levels of organotins in snails and in the fine fractions (< 63 microm) of the sediments they inhabit. The sampling locations were classified according to three levels of traffic densities of ships of > or = 100 gt per day passing within 15 Nautical miles of the sampling station, shipping levels being: high (> 10 ships day(-1)), intermediate (5--10 ships day(-1)), and low (< 5 ships day(-1)). Sampling stations were also classified according to presence or absence of a vertically stratified water column. In the snails the body levels of the butyltin metabolites MBT and DBT and the parent phenyltin compound TPT, were higher than those of TBT and PT metabolites. In the sediment, the parent compounds and the mono-substituted metabolites MBT and MPT were present in the highest concentrations. The highest body levels of all organotin compounds and the highest imposex indices for the common whelk were found at those locations in the Southern Bight and the German Bight that had a high shipping density as well as a homogeneously mixed water column during the whole year. At these locations sediment levels of organotins were also higher than at other sites. In contrast, the body levels of organotins were low and imposex was sometimes even completely absent in snails from stratified deep-water stations in the Skagerrak, despite a very high shipping density in the entrance area of the Baltic. In sediments from stratified locations with low or intermediate shipping densities, organotin compounds were below or close to their respective limits of detection. These stations were located in areas with a stratified water column during the whole year. The results can be explained by postulating a much higher resistance for dissolved organotins to migrate through a pycnocline. Organotins could only transgress through a pycnocline when adsorbed to settling particles that manage to transgress the boundary between layers. N. antiqua could only be obtained in sufficient numbers from deeper water stations, which almost all had a stratified water column. At stations where both snail species were obtained and imposex was present, the imposex index was higher in the red whelk. Hence N. antiqua seems to be the more sensitive species of the two. In the red whelk, imposex development increased with shipping density too, though in the smaller samples the trend was not significant. Average biota-sediment accumulation factors (BSAFs; normalised for lipid content in snails and TOC content in the fraction < 63 microm in sediments) for Buccinum ranged from 0.4 to 1.0 for butyltins and were similar to literature values reported for TBT in other marine species. Higher average BSAF values were found for phenyltins 1.5 (MPT) to 17 (TPT). The high values for TPT match the ranges expected from equilibrium partitioning concepts of persistent hydrophobic compounds. The ratio of live snails to the total number of live snails plus empty shells ranged between 2.5 and 93%. This parameter might be a useful indicator to compare past and present densities of populations of both species in different areas of the North Sea.     

Stress protein expression in Ampelisca abdita (Amphipoda) exposed to sediments from San Francisco Bay

Stress proteins (heat shock proteins, hsps) form part of the cellular protein repair system, and are induced by a wide variety of Stressors. To determine their suitability as tools for assessing sublethal sediment toxicity, we measured levels of members of the stress protein families hsp60 and hsp70 in benthic estuarine amphipods (Ampelisca abdita) exposed to sediments from 23 different sampling sites in San Francisco Bay for 10 d. Concentrations of sediment-associated xenobiotics were determined. Per cent survival was recorded and surviving animals were analysed for stress proteins using western blotting techniques. An inverse correlation (r² = 0.44) was seen between amphipod survival and hsp64 levels, and hsp64 levels were positively correlated with concentrations of total polycyclic aromatic hydrocarbons (PAHs) (r² = 0.5). Principal component analysis revealed that amphipod mortality was linked to a combination of several PAHs (phenanthrene, fluoranthene, pyrene, benzo(a)pyrene) and di-n-butylphthalate at southern San Francisco Bay sites. At northern San Francisco Bay sites, negative correlations were found between hsp64 levels and organotin compounds (MBT, DBT, TBT), and between hsp71 levels and the PAHs, benzo (b,k)fluoranthene and benzo(G,H,I)perylene, suggesting an inhibitory effect of these compounds on stress protein expression.     

Chronic toxicity of tributyltin on development and reproduction of the hermaphroditic snail Physa fontinalis: Influence of population density

Tributyltin (TBT) is toxic to aquatic organisms and occurs widely in sediments and surface waters of American and European rivers and lakes. This study investigated TBT effects on development and population growth rate (r) of the common, hermaphroditic European freshwater snail Physa fontinalis. Egg ropes of similar age (1-3 days old) were exposed to a control (solvent only) and nominal concentrations of 0.01, 1.0 and 10 microg TBT l(-1) in triplicate. Hatching and mortality were recorded during 0-40 days of exposure. At day 40, 18 juveniles were randomly selected from each concentration (i.e., six from each test vessel) and individually exposed to the same concentration of TBT in 50 ml beakers. A cohort of 20 juveniles was allowed to continue developing in the original test vessels, so that individual and grouped results could be compared. Mortality and reproduction were recorded at 48-h intervals throughout the study period (110 days). Abnormal embryonic development was observed at 1 and 10 microg TBT l(-1). Although 50% of eggs hatched at 10 microg TBT l(-1), all these hatchlings failed to survive. Survivorship of hatchlings was significantly reduced by TBT at 1 microgl(-1). In general, there was a delay in egg production in isolated snails when compared with the grouped snails. Survival, fecundity and population growth rate (r) were reduced in both individual and grouped P. fontinalis at 1.0 microg TBT l(-1). Only a decline in r was observed in snails exposed individually to 0.01 microg TBT l(-1).     

我国东南沿海3港口有机锡污染的调查

利用顶空固相微萃取与气相色谱表面发射火焰光度检测法于2001年11月至2002年8月对我国东南沿海厦门、汕头和惠阳3个大型港口21个站位的水样、底泥和生物样的有机锡污染现状进行调查.结果表明,绝大多数样品的一丁基锡(MBT)含量最高,三丁基锡(TBT)次之,二丁基锡(DBT)大多低于检测限.水样的TBT含量实测值从低于检测限至9.8ng/dm3,泥样的为0.3~174.7ng/g(干重),生物样的为2.1~23.0ng/g(湿重).水样TBT含量均值以惠阳港的为最高,泥样和生物样的均以厦门港的最高.影响有机锡含量及其空间分布的主要因素有港口船舶吞吐量、水文状况、季节和与大型码头的距离.关联的海产腹足类性畸变调查结果发现,我国沿海有机锡污染比较普遍和严重,已对生态系统产生实质性的负面生态效应.     

Stramonita haemastoma as a bioindicator for organotin contamination in coastal environments

Stramonita haemastoma was investigated as a suitable bioindicator of TBT and TPhT contamination in the tropical Atlantic Ocean by: 1. Imposex induction in healthy females after inoculation with TBT and TPhT in the laboratory; and 2. Determining incidence of imposex in S. haemastoma collected from areas with various levels of tributyltin (TBT) and triphenyltin (TPhT) and determining the concentrations of these chemical in its tissues and that of its prey, the mussell Perna pernas. Imposex intensities and organotin concentrations in tissues showed good correlation, indicating S. haemastoma as a reliable bioindicator of TBT and TPhT contamination in coastal waters. Body burden threshold of TBT and TPhT for imposex induction was estimated to be 10-20 ng g(-1).     

Variation in organotin accumulation in relation to the life history in the Japanese eel Anguilla japonica

In order to examine the ecological risks caused by organotin compounds (OTs) in diadromous fish migrating between sea and freshwaters, tributyltin (TBT) and triphenyltin (TPT) compounds and their breakdown products were determined in the catadromous eel Anguilla japonica, which has sea, estuarine and river life histories, collected in Japanese sea, brackish and freshwaters within the same region. Ontogenic changes in otolith strontium (Sr) and calcium (Ca) concentrations were examined along the life history transect to discriminate the migration type. There were generally three different patterns, which were categorized as ‘sea eels’, ‘estuarine eels’ and ‘river eels’ according to the otolith Sr:Ca ratio. The concentrations of TBT in silver eels (mature eels) were significantly higher than that in yellow eels (immature eels), and the percentages of TBT were also higher in silver eels than in yellow eels. A positive correlation was found between TBT concentration and the gonad-somatic index (GSI). It is thus considered that silver eels have a higher risk of contamination by TBT than yellow eels. TBT and TPT concentrations in sea eels were significantly higher than those in river eels, while no significant differences were observed in TBT and TPT concentrations in estuarine eels compared to sea and river eels. These results suggest that sea eels have a higher ecological risk of OT contamination than river eels during their life history, and the risk of OTs in estuarine eels is considered to be intermediate between that of sea and river eels. Positive linear relationships were found between Sr:Ca ratios and the concentrations of TBT and TPT. Therefore, these results suggest that the ecological risk of OTs increase as the sea residence period in the eel becomes longer. TBT and TPT concentrations in sea eels were significantly higher than those in river eels even at the same growth stage. Thus, it is clear that migratory type is the most important factor for OT accumulation during the life history.     

三丁基锡对褐菖鮋精巢性激素受体表达的影响

三丁基锡(Tributyltin,TBT)能够影响鱼类生殖功能,而有关TBT对鱼类生殖细胞发育至关重要的雄激素和雌激素受体的影响还未见报道。本实验以海洋经济鱼类褐菖鲉(Sebastiscus marmoratus)为对象,研究环境水平TBT(1,10和100ng/L)对精巢雄激素和雌激素受体表达的影响。结果表明,TBT暴露能够抑制褐菖鲉精巢发育和精巢雌激素受体蛋白的水平,并且发现雌激素受体主要定位于精巢精小叶腔间隙。小叶腔间隙的雌激素受体蛋白水平降低可能影响支持细胞和间隙细胞的正常功能,从而影响精巢的正常发育。TBT暴露对雄激素受体的表达并没有显著的影响。该结果为全面了解TBT产生鱼类生殖毒性效应、途径和机制提供了新的重要的资料。     

温度对光棘球海胆不同发育阶段的影响

于１９８８－１９９０年进行水温（０－３０℃）对光棘球海胆不同发育阶段的影响的试验。结果表明，水温对光棘球海胆各发育阶段的生长等均有显著影响，并且，不同发育阶段对水温的要求不同。其中，低于５℃或者高于２６℃时，受精卵不发育；低于１５℃或者高于２４℃时，浮游幼体发育不正常；低于０℃或者高至３０℃时，幼海胆难以生存，生长适温在１６－２２℃；成海胆，０℃时活力显著减弱但短期内无死亡，３０℃则大量死亡，生长     

Contamination of organotin compounds and imposex in molluscs from Vancouver,Canada

Gastropods and bivalves were collected at 15 sites at Vancouver and Victoria, Canada between 24 May and 7 June, 1999, to establish tissue concentrations of butyltin and phenyltin compounds, to record imposex symptoms in gastropods, and to assess the present status of organotin contamination around Vancouver. No neogastropods (such as Nucella lima) were found around Vancouver. Neogastropod populations could have been extirpated by severe TBT contamination in Vancouver, as relatively high concentrations of TBT were detected in tissues of Mytilus trossulus from Vancouver, and the neogastropods distributed in Vancouver might be sensitive to TBT. Recovery from imposex, however, was observed in neogastropod populations from three sites at Victoria and Mission Point. TBT contamination has continued around Vancouver, arising from continuous use of TBT in antifouling paints for vessels larger than 25 m in length; however, TBT has decreased around Victoria and Mission Point. Different patterns of TBT accumulation in tissue were observed among the bivalve species from Vancouver. The highest TBT concentration detected in Tresus capax suggested some possible adverse effects. TBT was the most predominant butyltin component in almost all bivalve specimens surveyed, suggesting a low rate of TBT metabolism. Phenyltin compounds were not detected in any molluscan specimens in this study.     

The effect of tributyltin upon steroid titres in the female dogwhelk, Nucella lapillus, and the development of imposex

Exposure of female Nucella lapillus to tributyltin (TBT) in seawater at a concentration of 40 ng Sn/litre led to accumulation of TBT in the tissues, and an increase in penis length compared to control animals. Investigation of the steroid concentrations by radioimmunoassay revealed a significant increase in testosterone after 28 days exposure to TBT. No significant effect was noted upon the amounts of progesterone or estradiol-17β. When testosterone was injected into female N. lapillus in the absence of TBT, penis length was found to increase significantly. These observation suggest that there may be an association between the change in testosterone titre in response to exposure to TBT and the development of imposex in the dogwhelk.     

Dumpton syndrome reduces the tributyltin (TBT) sterilising effect on Nucella lapillus (L.) by limiting the development of the imposed vas deferens

TBT induces imposex and sterilisation in female Nucella lapillus. Interestingly, there are populations where individuals (both males and imposexed females) may suffer from a genetic aberration [Dumpton Syndrome (DS)] which results in the development of no penis (i.e. aphally). This anomaly confers a so far unexplained protection against TBT. Six populations with contrasting DS frequency were sampled; the imposex stage in females and the mean calibre of every vas deferens (VDC) were assessed. While the sex ratio in the 600 specimens examined was close to 1, aphally was more frequent in females than in males (31 and 7%, respectively). VDC was significantly higher in normal than in aphallic (DS) specimens, independently of sex and/or site. It is concluded that the vas deferens imposed by TBT onto DS females is less prone to develop thick enough so as to interfere with normal egg laying.     

Exploring the use of caged Nucella lapillus to monitor changes to TBT hotspot areas: a trial in the River Tyne estuary (UK)

Caged dogwhelks (Nucella lapillus) and mussels (Mytilus edulis) were placed in situ at sites along the River Tyne (UK) in order to investigate the potential for monitoring any change in tributyltin (TBT) mediated effects. After 6 months the development of imposex was investigated in the dogwhelks and concentrations of TBT were determined in the whole tissues of both species. Sites within the estuary showed a high degree of imposex, whilst those at sites North and South of the estuary mouth exhibited significantly lower induction. Concentrations of TBT measured in the dogwhelk and mussel tissues showed the same pattern. The success of the caging technique, occurrence of imposex at other UK sites and the need for further monitoring at TBT impacted locations in the light of current international controls on the use of TBT-based antifouling paints on sea-going vessels are discussed.     

Assessing site-specific effects of TBT contamination with mussel growth rates

During nine field transplant tests in San Diego Bay (1987–1990), juvenile mussels were exposed to mean concentrations of tributyltin (TBT) in ambient seawater ranging from 2 to 530 ng liter⁻¹ for 12 weeks under natural conditions. A total of 79 cages with 18 mussels each were monitored at 18 different sites. Growth and seawater TBT concentrations were measured weekly or on alternate weeks (biweekly). Mean growth rates ranged from 17 to 505 mg week⁻¹ (0·2 to 2·5 mm week⁻¹). Accumulation of TBT in mussel tissues was measured at the end of each 12-week test exposure and ranged from 0·1 to 3·2 μg g⁻¹ TBT wet weight. The frequency of the measurements and the integration of chemical and biological measurements improved the accuracy of the assessment over more traditional approaches. Growth was significantly related to seawater and tissue TBT. The statistical relationships with growth effects were used to estimate chemical effect zones for TBT in San Diego Bay. Site-specific differences were distinguished by additional statistical analyses and consideration of environmental significance.