深圳大鹏湾和大亚湾近岸海水及潮间带动物的有机锡污染

调查了深圳大鹏湾及大亚湾近岸海水及其潮间带动物有机锡的污染状况.结果显示,大鹏湾海水中三丁基锡(TBT)和二丁基锡(DBT)的含量分别为21.13-25.03和10.22-18.68ng·L-1;大亚湾中海水中TBT和DBT的含量分别为nd(低于检测限)-7.63和nd-8.56ng·L-1,所有水样均未检测出单丁基锡(MDT).大鹏湾潮间带软体动物(近江牡蛎Ostrea rivularis Gould、团聚牡蛎Ostrea glomerata Gould、单齿螺Monodonta labio等)体内TBT、DBT、MDT、三苯基锡(TPT)的含量分别为3.02-26.48、nd-2.65、nd-1.57、13.10-164.08ng·L-1(湿重);大亚湾潮间带软体动物体内TBT、DBT、MDT、TPT的含量分别为nd-17.67、nd-1.50、nd、nd-17.66ng·L-1(湿重).与国内外其他海港水体和软体动物的调查结果相比,大亚湾受有机锡污染的程度相对较轻,但大鹏湾的污染程度则不容忽视.由此可见,我国应尽早制定法规限制有机锡类化合物的应用.     

胶州湾水体、浮游生物和沉积物中的锡

对胶州湾水体、浮游生物、悬浮颗粒物和沉积物中锡的测定、形式、生物累积等进行研究。不同季节(1987年和1988年)的水体、浮游植物和沉积物测定表明:1.水体总还原无机锡和总锡含量分别为4.2～38.8ng/dm~3,65.6～209ng/dm~3;浮游植物总锡含量为22.4～414mg/kg(干重);沉积物总锡含量为0.015～0.98mg/kg(干重),且在胶州湾港口区测得水体总锡的最大值209ng/dm~3。以上结果与目前世界其它海域、河口类似。2.有些区域有机锡含量已达到或超过某些生物的致毒阈值(对双壳类,其TBT≤0.1μg/dm~3)从而引起水质恶化。3.水体总锡含量与悬浮颗粒量密切相关;浮游植物对锡的生物富集因子高达10~5,说明无机或有机颗粒及生物体在水体锡的循环迁移过程中起重要作用。     

三丁基锡对秀丽隐杆线虫生殖能力的多世代毒性效应

三丁基锡(Tributyltin, TBT)是一种有机锡化合物,曾广泛用作船舶防污涂料杀生剂。尽管已经于2008年全面禁止在防污涂料中使用有机锡化合物,但环境中有机锡含量仍处于很高水平。TBT可以导致鱼类、哺乳动物体内脂肪积累增加,具有"肥胖因子"效应;TBT暴露可以使腹足类发生性畸变,对鱼类、哺乳动物造成生殖损伤。然而,关于TBT暴露对生物生殖能力的多世代毒性效应还未见报道。秀丽隐杆线虫(Caenorhabditis elegans)在土壤中广泛分布,在分解有机物和物质循环中发挥重要作用。秀丽隐杆线虫生活史短,可在短时间内获得大量子代,是理想的三丁基锡的多世代毒性效应研究对象。因此,本文以秀丽隐杆线虫为实验生物,研究TBT对其生殖能力的多世代毒性效应。研究结果如下:1 ng/L、10 ng/L、100 ng/L、1000 ng/L TBT暴露秀丽隐杆线虫48 h,对秀丽隐杆线虫的生殖能力具有显著抑制作用,并且可以传递到未暴露的子代(F1-F3代)。与对照组相比,1000 ng/L TBT暴露组F0代、F3代怀卵数分别减少23.53%、15.15%,子代数分别减少23.53%、15.15%;且阴门结构畸形率显著上升。推测子宫内怀卵数减少是子代数量减少的主要原因,而阴门结构的畸形可以使产卵行为受损,进一步加剧TBT对秀丽隐杆线虫生殖能力的抑制作用。本研究为有机锡防污涂料的污染治理提供理论依据。     

厦门海域水体中有机锡的存在形态与含量分布

利用固相萃取-气相色谱-火焰光度检测(SPE-GC-FPD)对厦门海域表、底层海水中的有机锡化合物进行了分析检测。其中表层海水中检出的有机锡化合物以二丁基锡(DBT)为主,底层海水中以三丁基锡(TBT)为主,且TBT的浓度显著高于表层水。表层海水中总有机锡浓度在129.1—4 826.8 ng(Sn).L-1之间,底层海水则分布在321.6—1 954.5ng(Sn).L-1之间。结果显示,厦门港内及同安湾附近海域水体中的有机锡浓度远高于九龙江口及厦门西南海域,这与厦门海域船舶活动和网箱养殖密切相关。通过对鼓浪屿站点表层海水中有机锡化合物15 h的连续监测,推测光照对水体中有机锡的降解影响显著。     

浙江沿海贝类体内有机锡化合物分布特征与风险评价

为了探讨浙江沿海贝类体内有机锡的存在形态及分布特征,采用戊基化格氏衍生GC-FPD方法测定了沿海六县(市)采集的双壳贝类体内3种丁基锡和3种苯基锡化合物含量,并采用风险系数法进行了健康风险评价。研究表明,苯基锡是贝类体内有机锡的主要污染物,含量范围为nd~203.6 ng·g^-1(干重),以二苯基锡为主。丁基锡总含量范围为nd~8.2 ng·g^-1(干重),以三丁基锡为主。贝类中贻贝对有机锡的富集能力较强。不同区域贝类体内的有机锡主要来源于海运船舶的防污涂料。健康风险评价结果表明,浙江沿海贝类对食用人群的健康是安全的。     

粤东柘林湾表层沉积物中的多环芳烃

近岸海域是绝大数污染物的最终归宿,其中多环芳烃(PAHs)的污染目前已成为国内外环境问题的焦点之一[1~3].20世纪80年代以来,国内外对河口湾、港湾、近岸海域等海洋环境中PAHs的含量、组成、分布、归趋及来源等做了大量的调查[4~15].比如,中国科学院广州地化所对珠三角水域和厦门大学对厦门港一带均做了大量的工作,结果发现表层沉积物中16种优控PAHs总量在珠江口达到156~9220 ng/g,闽江口为175~817ng/g,厦门西港则在196~675 ng/g之间,证明我国东南沿海主要河口及港湾沉积物中的PAHs污染已经达到中等水平[13~15].     

有机锡对金藻（Dicrateria sp.）的毒性效应

研究了有机锡对金藻的毒性效应 ,结果表明 ,三丁基锡 (TBT)和三苯基锡 (TPT)在低浓度的情况下 ,即可限制金藻细胞的生长和存活。室内一次培养研究显示 ,该 2种有机锡化合物对金藻表现出很强的毒性 ,对生长速率的 72 h半数效应浓度 EC50 分别为 0 .58和 0 .77μg/ dm3。     

海产腹足类有机锡化合物的检测方法

三丁基锡(TBT)等有机锡化合物因其毒性及结构上的特点被广泛应用于船舶、网箱渔排等的防污涂料中.它的主要作用是在水体中持久地释放出可以有效杀死海洋污损生物的毒性物质,从而达到防护船舶、渔排等体表的目的[1],然而进入海洋环境的有机锡化合物在防污的同时也会影响到许多非靶生物,并对海洋生态系统的结构与功能产生严重的危害,被认为是迄今为止人为引入海洋环境毒性最大的物质之一[2～4].因此,检测海洋生物体内的有机锡含量成为对有机锡污染生态效应调查与研究不可缺少的手段[5～7].     

厦门西港表层沉积物中多环芳烃(PAHs)的含量分布特征及其污染来源

利用GC－FID对厦门西港1998年7月采得8个站位表层沉积物中的16种多环芳烃（PAHs)进行了分析。结果显示，16种多环芳烃总量分布范围为247－480ng/g，平均为367ng/g。与1993年的厦门港的分析结果相比较，多环芳烃的污染程度降低；同世界其他港口相比较，其污染程度相对较低。同时，分析了厦门港PAHs污染的分布特征及其可能的污染来源，表明其主要是由于人类的油污染及燃料燃烧引起的。     

胶州湾东部锡的输入、形态特征和生物地球化学过程

自1990年7月～1991年5月取样测量了胶州湾东部各形态锡的季节序列变化.溶解无机锡、有机锡和颗粒态锡的百分比表明了锡形态分布的区域特征及可能的输入.丰水期(7月),各形态锡出现异常高值(DISn76.7ng/dm3,DOSn546.1ng/dm3,PSn688.6ng/dm3),表明陆源输入的主要作用.随着湾内海水盐度升高,溶解态无机、有机锡呈现外海低值的特征,但颗粒锡占据了绝对比例.极高的颗粒物富集因子(8.5×104～2.2×105)和浮游生物富集因子(5.1×104～7.0×105),说明水体锡的强颗粒物活性和生物获得性,对排除无机、有机锡起重要作用.相反,沉积物中锡的甲基化则将是锡从沉积转入水体的重要途径.     

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.     

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     

厦门港中华哲水蚤卵型研究

对厦门港中华哲水蚤(Calanus sinicus)的卵型进行观察和研究,获得主要结果如下:(1)厦门港中华哲水蚤仅存在一种基本卵型,属于无鞘卵,但卵表面具有透明、柔软的胞膜(blister),胞膜呈褶皱结构;(2)胞膜可因外力而脱落,但胚胎仍可以正常发育;(3)在实验室水温为16~22℃条件下,受精卵均可正常孵化与发育;(4)胞膜的厚度有一定的变化,它随着水温的升高有减小的趋势.卵型分析与孵化实验均证实:厦门港中华哲水蚤不存在休眠卵(dormant egg)或滞育卵(diapause egg).     

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.     

TBT contamination of an artisanal subsistence fishery in Suva harbour,Fiji

The intertidal zone around the Suva Peninsula, Fiji, supports separate finfish and invertebrate subsistence fisheries. This important source of fresh marine food for many low-income families around metropolitan Suva is under threat from foreshore reclamation projects and from anthropogenic biochemical pollution. Damage to or loss of this invertebrate intertidal fishery would remove a significant area where urban dwellers can pursue this traditional (non-cash) means of seafood acquisition. In 1996, Suva Peninsula was considered for the development of a marina, hotel, aquarium, roads, walls, and other structures. There is also increasing evidence of a serious anthropogenic TBT (tributyltin) pollution threat to the local invertebrate fishery. Although this substance is well known to have ecologically deleterious effects, its use is unregulated in Fiji. The inputs are likely to be large commercial vessels, and in particular the shipyards around the west side of Suva Harbour, where TBT antifouling coatings are both applied and removed, the old paint debris being allowed to wash into the harbour. Inputs from small boats are probably less important as there are relatively few (<150 boats) but uses of TBT, as a wood treatment chemical, for example, may lead to other inputs (but these have not been investigated). Samples of Anadara antiquata and Gafarium tumidum contained high levels of TBT ranging from <50 ng TBT gm⁻¹ to 240 ng TBT gm⁻¹. Samples of the edible bivalve G. tumidum taken from the Lami Dump intertidal zone had accumulated 10,500 ng TBT gm⁻¹. The values of TBT in Suva Harbour and Laucala Bay sediments have reached levels that are among the highest in the world and indicate that these sediments are functioning as geochemical sinks for this toxic organotin substance.     

Embryotoxicity of butyltin compounds to the sea urchin Paracentrotus lividus.

Tributyltin (TBT) has been widely employed in marine anti-fouling paints as a biocide, although it represents a serious risk, particularly in estuarine and coastal water/sediment ecosystems. In this study, the embryotoxic effects of TBT and its degradation products, dibutyltin (DBT) and monobutyltin (MBT), were analyzed during the development of the sea urchin Paracentrotus lividus from post-fertilization to the pluteus stage, to better clarify ecotoxicological impact. The embryotoxicity of butyltins is concentration-dependent and increases proportionally with number of butyl groups. Significant growth reduction was observed at TBT concentrations as low as 0.01 microgram l-1; 1 microgram l-1 was the maximum concentration allowing embryos to reach the pluteus stage at 48 h post-fertilization. Development was blocked at the morula or blastula stage with higher TBT concentrations. DBT and MBT are less toxic: slowed development and a decrease in pluteus size occurred at 10 micrograms l-1 DBT and 0.5 mg l-1 MBT. Effects on both skeletal deposition and blocked embryonic development are suggested to be due to the interference of organotin compounds with intracellular calcium homeostasis.     

Tributyltin impacts in Galapagos Islands and Ecuadorian shore: Marine protected areas under threat

Imposex incidence and biometric parameters were investigated in six muricid species along of 1200 km of Ecuadorian shore and in Galapagos archipelago. The obtained data, were compared to previous studies performed in the same area in 2009. The results showed that moderate imposex levels still occur in coastal areas of Ecuador, even after global TBT ban. However, a reduction in imposex parameters was detected in the sampled sites, indicating probably relationship to the global TBT ban issued by IMO at 2008. On the other hand, the levels currently reported in present study indicates that TBT environmental concentrations are still high enough to produce biological effects in studied areas. In addition, imposex incidence in four muricid species from Galapagos islands were detected suggesting that this marine protected area is under threat of antifouling contamination. These findings, after TBT global ban, denotes that current regulations and conservation plans still need to address such an issue and incorporate more restrictive management rules, particularly in complex coastal areas, vulnerable and unique systems such as the Galapagos Islands.     

Imposex and surface sediment speciation: a combined approach to evaluate organotin contamination in Guanabara Bay, Rio de Janeiro, Brazil

An integrated biological-chemical survey of organotin compounds was carried out in Guanabara Bay, the second most important Brazilian harbor complex. The biological survey revealed high levels of imposex in Stramonita haemastoma populations. Inside the bay values of relative penis length index from 42.7 to 107.6 and vas deferens sequence index from III to VI were found, while organisms collected outside the bay had values ranging from <0.1 to 35.2 and from 0 to II. None of the females sampled inside the bay were normal and imposex was found in all stations. Surface sediments in the bay are contaminated by tributyltin (10-522 ng/g d.w.) and triphenyltin (<3.9-39.4 ng/g d.w.) with greater concentrations close to shipyards and marinas. The observed predominance of parent compounds (TBT and TPT) is commonly found when recent inputs occur, but may also indicate slow degradation processes in the anoxic conditions of these sediments. To our knowledge, this is the first report of a combined imposex-sediment approach to evaluate organotin contamination in marine environments of South America, and also the first report of TPT detection in environmental matrices in this region.     

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.