【作者】 曹丹丹；

【导师】 江桂斌；

【作者基本信息】 中国科学技术大学 ， 环境科学， 2008， 博士

【摘要】 丁基锡作为船体防污涂料添加剂、聚氯乙稀塑料添加剂、工业催化剂等大量使用,对海洋环境造成严重污染,并引起海洋生物的性畸变。研究表明有机锡污染多数发生在水体环境中,尤其是沿海区域的水体、底泥、海洋生物中丁基锡的浓度相对较高。由于生物累积作用,一些海产品中有机锡的含量较高,对食用这些有机锡污染海产品的人群造成潜在健康危害。因此,对软体动物中丁基锡污染的研究具有重要的意义。标准物质是实施实验室质量保证和质量控制体系的重要手段,研制标明形态含量的标准参考物质是一项困难的任务,需要花费大量时间和人力。从无机向有机、从总量向形态的发展是标准物质的发展趋势。我国标准物质研究领域中有机金属形态成分分析标准物质的研究刚刚起步,目前尚未有丁基锡标准物质。本论文针对我国环渤海地区环境中丁基锡污染比较普遍的现状,在软体动物中丁基锡分析测定的前处理方法、环渤海地区软体动物中丁基锡污染状况及软体动物中丁基锡成分分析标准参考物质研制等方面开展了一系列工作。丁基锡分析测定方法是研究丁基锡在环境中的污染状况及其环境行为的前提。对格林试剂衍生结合气相色谱-表面发射火焰光度检测器(GC-QSIL-FPD)中样品前处理方法的消解、萃取以及净化等步骤进行了条件优化。该优化提高了测定生物样品中丁基锡的消解效率和萃取效率,减少了前处理过程中的杂质成分,缩短了前处理过程的时间。这为后续研究提供了基础。对2005到2006年对环渤海区域软体动物中的丁基锡污染状况进行了调查研究。发现丁基锡化合物污染普遍存在,丁基锡的含量范围为＜8.8到629.2 ngSn/g干重(平均30.1 ng Sn/g干重),在所采集的软体动物中丁基锡检出率为70%。在本调查中发现,不同种类的软体动物具有明显不同的丁基锡富集能力,分析表明砂海螂的富集能力显著高于其它物种。参照国家一级标准物质技术规范研制了软体动物砂海螂中成分分析标准参考物质。所使用方法为经过条件优化的格林试剂衍生结合气相色谱-表面发射火焰光度检测器对标准物质中丁基锡形态化合物进行分析。采集的砂海螂经去壳、清洗、匀浆、冷冻干燥、球磨前处理步骤之后,混匀装瓶。进行了瓶内和瓶间均匀性检验及-20℃存放条件下6个月内的稳定性检验,结果表明均匀性和存放6个月内的稳定性良好。对该标准参考物质的定值进行了初步探索。更多还原

【Abstract】 Tributyltin (TBT) has been used worldwide in antifouling paints for ships and fishing nets since the mid-1960s, and its derivatives dibutyltin (DBT) and monobutyltin (MBT) were mostly used as stabilizers in polyvinyl chloride and as catalysts in industrial processes. Aquatic pollution by butyltin compounds has been of great concern due to their severe impacts on non-target marine organisms such as shell malformation in oysters and imposex in gastropods. High concentrations of BTs in seawater, sediments, and biota samples have been detected in China. Further research and date would be helpful to understand the status of BTs pollution and its temporal and historic variations.TMAH alkaline extraction and HC1-THF acid extraction were investigated based on Grignard pentylation- gas chromatography coupled with flame photometric detection using quartz surface-induced luminescence (GC-QSIL-FPD). The results revealed that HC1-THF solution is suitable for extraction of BTs in mussels. Dichloromethane, benzene and hexane were compared as extracting organic solvents for liquid-liquid extraction, which indicate that hexane exhibits high extraction efficiency. The LODs of the developed method were 2.6, 2.9, 3.3 ng Sn/g for MBT, DBT, and TBT, respectively. The spiking recoveries for BTs were in the range 102.0-106.4%. The new developed method improves the digestion and extraction efficiency, eliminates the interference and minimizes the pretreatment time.10 areas around the Chinese Bohai coast, individuals including 13 kinds of mollusks were collected during the period of 2005-2006 for the investigation of spatial distribution and temporal variations of butyltin compounds. BTs including TBT and its derivates, DBT and MBT were quantified by gas chromatography/flame photometric detection after extraction and Grignard derivatization. BTs compounds were widely existed in the collected samples, with its ranges from <8.8 to 629.2 ng Sn/g dry weight. The pollution levels of different sampling sites and the enrichment capacity of different mollusk species were discussed. The results indicate that the samples collected from Shouguang, Yingkou, and Penglai was seriously contaminated by BTs. The BTs levels in bivalves were higher than that in snails. Mya arenaria was found to have strong ability of butyltin accumulation compared with the other sampled bivalves in the corresponding batches, which was was potentially a biomarker to indicate organotin pollution in coastal aquatic environment. The wide occurrence and serious pollution of BTs in seafood indicated a potential danger for the health of the local people who cared for these foods.A new biological certified reference material, Mya arenaria, for butyltins analysis has been prepared and certified. Candidate biological material was acquired at Hongqiao and Dazhongsi Market, Beijing, which were collected from Dalian. After homogenization, freezen-drying, grinding, sieving and mixing, the material was sterilized withγ-ray irradiation. The material was re-mixed and packaged into 110 glass bottles (10 g each) and these were stored in a freezer at -20℃. Certification was performed by use of acid extraction, Grignard derivatization, followed by GC-QSIL-FPD analysis.更多还原