有机锡化合物测定方法研究进展

总结了有机锡化合物常用的测定方法，包括气相色谱－火焰光度法，气相色谱与原子吸收联用，气相色谱－微波等离子体发射光谱法，气相色谱－质谱法以及液相色谱与名种检测方法联用等。对样品前处理、衍生化方法、色谱分离及测定等也进行了讨论     

Growth of Plants on TBT-contaminated Harbour Sludge and Effect on TBT Removal (10 pp)

Background Worldwide, large amounts of sediments have to be dredged annually from waterways and harbours. These sediments are sometimes polluted with a variety of toxic compounds. In some countries, including Belgium, the load with the biocide tributyltin (TBT) from ship coatings prohibits the dumping of harbour sludge into the sea. Land-based dumping is a commonly used alternative. Objective This research investigated the feasibility to use land-deposited harbour sludge for plant production. In a field trial, the growth of 38 more or less salt-tolerant plant species on low and high TBT-contaminated sediments was studied. The elimination of TBT from sludge with and without vegetation was compared. The uptake of TBT and its degradation products di- and monobutyltin (DBT and MBT) into harvest products under field conditions was determined. - Experimental Set-up. Sediments dredged in May 2003 from the brackish waters of the port of Antwerp were analysed in the laboratory for soil texture, pH, electroconductivity, sodium, magnesium, potassium, calcium, ammonium, nitrate, total nitrogen, chloride, sulphur and the organotins TBT, DBT and MBT. The sediments were lagooned for one year to dewater, desalinate and improve their structure. Salt-tolerant domestic and wild plants were selected and sown in May 2004. In August 2004, plants were harvested and the produced biomass was determined. Samples were taken from vegetated and non-vegetated top and bottom sediments and from plants growing above soil and analysed for TBT, DBT and MBT. Results The fresh sediments showed a good supply with nutrients and a neutral pH, but were rather saline (EC 14 mS cm-1 of the saturated paste extract). The salinity decreased to 3.7 mS cm-1 during lagoonation. The high and the low contaminated sediment had initially 43 and 1.6 mg TBT kg-1 dry weight, respectively. Besides TBT, several other contaminants were present in the sediments at critical levels. The biomass production of the plant species from the field trial ranged from 0.2 to 13 tons dry mass per hectare. Plants performing excellently were barley, sorghum, rape seed, a clover/grass mix and reed. If at all, a positive influence of TBT on plant growth was seen. TBT was degraded significantly faster (>40%) below barley. The uptake of TBT, DBT and MBT into stem and leaves of reed, grass and clover was very low, but measurable and not related to concentrations in soil. No uptake of TBT or its metabolites into corn of barley was found. Discussion This study confirmed former results: the toxicity of TBT to higher plants is low, and even high levels in soils would not be a hindrance for crop production. The removal of TBT seemed to be increased by both lagooning and plant growth, although the target values for sea dumping in use in certain European countries were not reached. A plausible explanation for the faster degradation of TBT under vegetation is that oxygen is a limiting factor, and plants dewater the soil, thus aerating it. The uptake of the organotins TBT, DBT and MBT into harvest products is probably due to attached soil particles. Conclusions To summarize, barley was the optimal species: it grew very well despite the salinity of the dredged sediments, it had a significantly positive effect on TBT removal; it showed no measurable uptake of TBT or the other butyltins into the harvested product; and it is a cash crop well established in European agriculture. Outlook The amounts of dredged sediments are high, and good soils are becoming increasingly rare. The feasibility of using dredged sediments for non-food production, such as energy crops, should be investigated by a critical risk assessment.     

我国海水水质基准的构建:以三丁基锡为例

我国近岸海域污染形势严峻、污染物种类繁多、生态健康风险复杂,现有的海水水质标准难以满足当前海洋环境污染评价、管理和监控的需求,亟需适宜我国海洋区系特征的海水水质基准作为水质标准修订与制定的理论依据.借鉴美国、欧盟和荷兰等国家水质基准的制定方法,提出了构建我国海水水质基准的思路,并给出了数值型双值基准的数据要求、定值方法和相应的计算模式等.以三丁基锡化合物(TBT)为例,按照论文建立的方法,计算了保护我国海洋水生生物的TBT基准.结果表明:我国TBT化合物海水水质基准高值(HSWC)和海水水质基准低值(LSWC)分别为0.43μg·L-1和0.002μg·L-1,与美国,加拿大和英国等国家的推荐基准值略有不同.研究结果将为我国海水水质基准的制定与研究提供帮助.     

Application of Neomysis awatschensis as a standard marine toxicity test organism in China

The small mysid crustacean Neomysis awatschensis was collected in the west coast of Jiaozhou Bay, Qingdao, China in 1992 and acclimated and cultured in laboratory conditions since then. Standard acute toxicity tests using 4--6 d juvenile mysids of this species were conducted and the results were compared with Mysidopsis bahia, a standard toxicity test organism used in the US in terms of their sensitivities to reference toxins, as well as their taxonomy, morphology and geographic distributions. Because of its wide distribution along the Chinese coast, similar sensitivity to pollutants as M. bahia, short life history, small size and the ease of handling, this study intended to use N-awatschensis as one of the standard marine organisms for toxicity testing in China. The species were applied to acute toxicity evaluations of drilling fluid and its additives, organotin TPT and toxic algae, and to chronic (life cycle) toxicity assays of organotin TPT and a toxic dinofalgellate Alexandrium tamarense, respectively. Using N. awatschensis as a standard toxicity testing organism in marine pollution assment in China is suegested.     

气相色谱-表面发射火焰光度检测法测定有机锡和有机锗化合物

本文将自行研制的GC-FPD测定系统用于有机锡和有机锗的形态分析.在最佳测定条件下,使用HP-1毛细管色谱柱和柱头进样方法,成功地分离了九种有机锡化合物和四种有机锗化合物.分别对样品的萃取、衍生方法以及仪器测定条件的优化等进行了讨论.并用本文所建方法分离和测定了环境样品中的有机锡化合物.     

海洋环境中的有机锡及其对海洋生物的影响

本文综述了有机锡化占物对海洋环境的冲击及其对海洋生物的影响，介绍了有机锡化合物的分析方法，讨论了有机锡污染的预防和控制措施，并展望了有机锡研究的前景。     

单纯形最优化法在流动注射-氢化物-石墨炉原子吸收法测定海水中有机锡中的应用

用单纯形最优化方法对流动注射-氢化物-石墨炉原子吸收法测定海水中有机锡的条件进行优化，计算简便，用较少的实验次数动态地调至最佳分析条件。     

长江口崇明渔港表层沉积物中丁基锡赋存特征及生态风险

在长江口及崇明岛沿岸渔港采集表层沉积物样品,通过超声萃取-乙基化衍生技术提取沉积物中的丁基锡化合物,用气相色谱-质谱联用仪分析沉积物中的丁基锡赋存特征。结果显示,在长江口的参考点沉积物中均未发现有机锡化合物,而在各调查的渔港沉积物中均检出丁基锡,总浓度在1.6~58.8 ng Sn·g-1(干重,以下同)之间变化。表层沉积物的三丁基锡(TBT)、二丁基锡(DBT)和一丁基锡(MBT)浓度范围分别为ND~28.7 ng Sn·g-1,ND~22.1 ng Sn·g-1,1.6~8 ng Sn·g-1。其中,堡镇港TBT污染水平最高;老滧港和奚家港口门处沉积物中TBT浓度与新河港差不多(平均为17.2 ng Sn·g-1),而在港口内部沉积物中均未检出TBT,仅有MBT残存。检出TBT的样点,均在大型渔船码头、客运游艇码头或船厂附近,其浓度均超过澳大利亚和新西兰推荐的TBT沉积物质量基准(ISQG)触发值,即5 ng Sn·g-1。同时各样点暴露浓度(PECsed)与预测无效应浓度(PNECsed)的商值均大于1,SQG和PECsed/PNECsed两个方面均反映了崇明岛渔业港口沉积物中的TBT存在生态风险。综上,长江口地区沉积物中有机锡化合物形态和浓度差异很大,码头或船厂附近沉积物中有机锡污染问题值得优先关注。     

克雷伯氏菌对三苯基锡的酶促降解特性

研究了肺炎克雷伯氏菌对三苯基锡(TPhT)的酶促降解性能,并对酶促反应影响因素的作用机制进行了探讨,以期为阐明有机锡的微生物降解机制提供实验依据.研究证明,菌体、分泌物和胞内降解酶均具有降解TPhT的能力,在30℃转速为130.rm in-1的摇床中避光处理2 h后,对3 mg.L-1TPhT的降解率分别为10.9%、5.3%和47.9%.影响因素实验表明,降解介质、pH、温度、TPhT浓度和金属离子均会对TPhT的酶促降解效果产生影响,其中TPhT酶促反应的最适pH和温度分别为8和50℃.Mg2+、Mn2+、Fe2+和Fe3+在合适的浓度范围内,均会促进TPhT的降解.当Mg2+的浓度为15 mg.L-1时,胞内酶对TPhT的降解率高达73.8%.金属离子的促进效果主要与其对酶的激活、作为电子受体或电子供体参与TPhT酶促降解等作用有关.TPhT的降解速率与其浓度呈现理想的线性关系.该反应的Vm ax和Km分别为0.15 mg.(L.m in)-1和47.1 mg.L-1.     

深圳蛇口港及深圳湾潮间带动物的有机锡污染

以异辛烷为萃取剂、四乙基硼化钠为衍生剂对样品进行同步化液-液萃取衍生反应,采用气象色谱-火焰光度检测法,研究了深圳蛇口港及深圳湾海域潮间带动物的有机锡污染状况。结果显示,所有站位采集的双壳类体内普遍检测出三苯基锡、三丁基锡及其降解产物二丁基锡,含量分别为127.1～349.1、6.3～380.8及2.7～99.9ng/g(湿重)。采自赤湾和东角头的渔舟蜒螺体内存在较高含量的三苯基锡567.3～651.6ng/g(湿重)。所有软体动物均未检测出单丁基锡。采自红树林的纹藤壶含127.1ng/g(湿重)的三苯基锡,但未检测出丁基锡。文章结果与国内外已有的相关数据比较表明,蛇口港潮间带动物已经受到较严重的有基锡污染,深圳湾的海洋生物也受到一定程度的污染。深圳湾红树林国家自然保护区对于生物多样性的维持及侯鸟的保护都极其重要,该海区的有机锡污染问题需要引起高度重视。