摘要
环境内分泌干扰物质及其引发的一系列环境问题已成为一个全球性的社会问
题,引起了世界各国尤其是发达国家政府和国际组织的广泛关注。TBT和TPT是
目前已知内分泌干扰物质中唯一的金属化合物,也是人为引入水环境最毒的化学
物质之一,对多种生物(包括人类在内)都有不同程度的毒害作用,许多国家已
将它们列入优先控制的黑名单中,同时对各种水环境的有机锡污染状况进行了大
规模的调查。我国目前还没有明确的限制有机锡使用的法律法规,缺少有机锡污
染的第一手资料,更没有长期的控制、监测与研究计划。从我国这方面已有的工作
来看,缺乏各种化学分离和灵敏有效的分析方法是制约这项研究广泛开展的原因
之一。针对这些特点,本论文以TBT和TPT及它们的代谢产物为研究对象,建立
了分析有机锡的GC-MS和HPLC-MS分析方法,利用建立的GC-MS方法分析测
定了我国不同水环境中有机锡的暴露水平,根据测定结果对渤海湾海水中TBT污
染的生态风险以及天津地区海产品和饮用水中有机锡污染对当地人群的健康风险
进行评价,最后提出了预防和控制有机锡污染的建议。
首先以固相微萃取和超声提取结合GC-MS检测,在本实验室建立了水样和生
物样品中ng级痕量有机锡的分析方法,并初步建立了同时分析TBT和TPT的
LC-ESI-MS法。其中水样中有机锡的分析方法包括同时分析DBT和TBT的顶空
SPME-NaBH4衍生-GC-MS方法和同时分析丁基锡和苯基锡的SPME-NaBEt4衍生
-GC-MS方法,生物样品中有机锡的分析方法为能同时分析丁基锡和苯基锡的
NaBEt4衍生-GC-MS方法。
利用所建立的分析方法分别对渤海湾、天津某自来水厂、北京高碑店污水处
理厂和长江三峡库区重庆至宜昌段的水样以及渤海湾部分水生生物的有机锡污染
状况进行了调查。对渤海湾水样的调查结果表明,渤海湾大多数水样中均含有较
高浓度的DBT和TBT,近岸丁基锡污染高于远海,渤海湾TBT污染主要来自船
只防污油漆的渗漏,而DBT除来自TBT降解外,还来自入海的陆地排污河。对天
津某自来水厂的调查结果表明,该水厂的水源受到有机锡污染,且污染存在明显
的季节性变化,从5月份到9月份污染是逐渐减轻的;从测定结果来看,传统的
自来水处理工艺能有效去除MBT和DBT,但对TBT和苯基锡去除效果较差。这
是第一次在饮用水中同时检测到MBT、DBT、TBT’、MPT、DPT和TPT六种有机
锡的报道。对北京高碑店污水处理厂的调查结果表明,该污水处理厂污水中存在
DBT和TBT污染,有时也会有MPT污染。传统的一二级处理和深度处理能有效
去除MBT和DBT,但对TBT和MPT的去除效果较差,与饮用水处理过程中观察
重庆大学博士学位论文
到的结果一致。对长江三峡库区重庆至宜昌段水样的调查结果表明,香溪河和望
龙门有机锡污染比较严重,其中香溪河DBT浓度达到416.sngsn几,MBT和MPT
的浓度分别为“.4和52.ongs可L;此外,大溪沟和晒网坝分别检测到33.4和
68.gngs可L的TBT,高于保护淡水生物的水质标准,因此这两地江水中的TBT会
对水体中的淡水生物产生慢性毒性影响。其他地方如清溪场和白帝城等地有机锡
污染相对较轻。这是第一次在长江水样中检测到MPT的报道。对渤海湾部分生物
样品的调查结果表明,大部分生物样品基本上都受到TBT和TPT污染,而它们的
代谢产物污染相对较轻。
结合前面的调查结果,采用风险商的评价方法分别对渤海湾部分水体中TBT
污染对该地区几种敏感水生生物繁殖发育影响的生态风险以及天津地区海产品和
饮用水对当地人群的健康风险进行了评价。评价结果表明:渤海湾大部分水体中
TBT污染对当地浮游生物细胞分裂、腹足动物性别发育以及牡蝠壳钙化均存在较
大的风险,对双壳类动物繁殖的影响稍小;天津地区海产品的有机锡污染可能会
对当地人群的健康存在风险,其风险来源主要是海产品中的TBT污染;天津某自
来水厂的自来水对当地居民的健康是安全的。根据本论文的研究结果,最后提出
了预防和控制有机锡污染的建议。
Endocrine disrupting chemicals (EDCs) and their environment problems have been a global problem, and widely received attentions from many countries, especially developed countries and international organizations. Tributyltin (TBT) and Triphenyltin (TPT) were the only metal compounds in known EDCs and were also one of the most toxic chemicals to the aquatic organisms, which do harm to many organisms, human included, so TBT and TPT have been appeared on the gray or black list in many countries, and their occurrence in aquatic environments were investigated on a large scale. At present, there is still no specific legislation controlling the use of TBT and TPT in China for lack of original data about organotins pollution, say nothing of long-term control, monitoring and research programs. One of main reasons to restrict this work is lack of effective chemistry separation and sensitive analytical procedures. In this paper, SPME-GC-MS were developed and applied to determine the concentrations of TBT, TPT and their
degrade products in different water environments, and that LC-ESI-MS was established for determination of TBT and TPT. Meanwhile, The occurrence of organotins in some aquatic organisms was also investigated. The ecology risk of TBT pollution in Bohai Bay and human health risk of seafood and drinking water for organotins in Tianjin were assessed. Finally, the control measures of organotins pollution in water environment were suggested.
First of all, analytical procedures for organotins in water and biological samples based on GC-MS were developed in the laboratory using solid phase micro-extraction and ultrasonic extraction for pre-treatment, which can well meet the requirement of environmental analysis. Thereinto, analytical methods of water included headspace SPME-GC-MS combined hydride generation with NaBFL, for DBT and TBT and SPME-GC-MS combined ethyl derivatization with NaBEti for butyltins and phenyltins. Moreover, a comprehensive analytical method based on LC-ESI-MS has been established for determination of TBT and TPT.
With the established methods, the occurrence of organotins in Bohai Bay, a Tianjin drinking water plant, Beijing Gaobeidian wastewater treatment plant, Three Gorges Yangtse River and some aquatic organisms from Bohai Bay were investigated. Experimental data demonstrated the widespread occurrence of organotin compounds in the selected water environments and aquatic organisms. Bohai Bay were widely
polluted by butyltins, and their levels were high near coastal areas and decreased towards off-shore. In this area, TBT mainly came from anti-fouling paints and DBT came from other sources besides TBT degradation. The data of drinking water plant demonstrated drinking water source were polluted by organotins, and MBT, DBT, TBT, MPT, DPT and TPT were detected simultaneously for the first time. Organotins pollution varied with season in this drinking water plant, and decreased from May to September. Results from wastewater treatment plant showed that most of organotins in municipal wastewater were DBT and TBT, and the highest level were 108.9ngSn/L and 59.8ngSn/L, respectively, sometimes relatively high levels of MPT were also found. From above data we can conclude that routine processes of water and wastewater can remove MBT and DBT effectively, but the removals of TBT and phenyltins were not good. The data from Three Gorges showed that XiangXi River were polluted by orgaontins seriously, with DBT, MBT and MP
T of 416.8, 66.4 and 52.0ngSn/L, respectively. Moreover, the concentrations of TBT in DaXiGou and ShaiWangBa were 33.4 and 68.9ngSn/L, respectively, which would do harm to fresh water organisms. There were relatively slightly pollution in other stations, such as QingXiChang and BaiDiCheng. It is the first time to found MPT in Three Gorges. The results of biological samples showed that the most of aquatic organisms were polluted by TBT and TPT, and no MPT and DPT were found.
According to investigated data above, the ecology risk of TBT pollution in Bohai Bay and human health risk of sea
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