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。     

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.     

金属离子对三苯基锡酶促降解的影响

研究了不同金属离子及其添加形式对肺炎克雷伯氏菌胞内酶和胞外酶降解三苯基锡的影响,以期为阐明有机锡的酶促降解机制提供实验依据.结果表明,菌体对K+、Mg2+、Cu2+、Ca2+、Fe3+具有良好的耐受能力,高浓度的Zn2+、Fe2+可能对菌体产生一定的毒害作用,从而影响其生长.适当浓度范围的K+、Mg2+、Zn2+、Cu...     

Adsorption and desorption of tetraalkyllead and dibutyltin compounds on contaminated soils

Adsorption and desorption of di-n-butyltin (IV) (DBT), tetramethyllead (TML), and tetraethyllead (TEL) on four types of soil were studied. Although, all K _d values for desorption are higher than the K _d values for adsorptions, which shows that the adsorption process is reversible, the lower percentages of desorption indicate that very low concentration of these organometallic compounds can be more easily leached from the soil. The adsorption ranging between 48.8% and 88.3% for DBT, between 9.1% and 38.3% for TEL, and between 24.9% and 44.2% for TML was measured. The desorption was obtained between 9.4% and 23.7% for DBT, between 19.3% and 38.9% for TEL, and between 21.5% and 32.7% for TML. These results show that the nonpolar (TML, TEL) organometallic compounds can be easier leached than the ionic forms (DBT). Adsorption kinetics and adsorption as a function of pH were also evaluated. DBT and tetraalkyllead adsorption equilibrium were reached after 12 and 24 h, respectively. The tetraalkyllead is strongly adsorbed at pH 7–8 and DBT at pH 6.     

三丁基锡和菲对鳗鲡的毒性效应（Toxic Effects of Tributyltin and Phenanthrene on Eels）

采用腹腔注射方式(每周1次,共5次)将生活于淡水或海水中的日本鳗鲡(Anguilla japonica)暴露于三丁基锡氯化物(TBTCl)和菲(Phe),以研究这两种污染物对鳗鲡的毒性效应以及该效应与鱼体所处环境盐度的关系.鳗鲡暴露于TBTCl或Phe1w后,其肝脏和脾脏的组织结构就已发生明显病变,且病变程度随着暴露时间的延长而加剧,其中海水鳗鲡比淡水鳗鲡表现更为严重;但肝体指数(HSI)和性腺组织结构均无明显变化.暴露于TBTCl4～5w后,海水鳗鲡肝脏的谷胱甘肽-S-转移酶(GST)活性比对照组显著升高,而淡水鳗鲡组无明显变化;暴露于TBTCl或Phe3w后,淡水鳗鲡的血浆皮质醇水平显著升高,但海水鳗鲡组无明显变化.TBTCl和Phe对淡水或海水鳗鲡的血浆雌二醇(E2)水平均无明显影响.以上结果表明:有机锡和菲对鳗鲡的肝脏、脾脏有毒性作用,对皮质醇分泌具有内分泌干扰作用,且该效应与暴露时间和鱼体所处环境盐度有关.