摘要
高雄港為台灣第一大港，根據以往研究顯示港口常為有機
錫污染嚴重的地方，隨著船隻頻繁的往來，添加在船舶底部的有效抗附劑三丁基錫(TBT)會釋放到海水中，造成港口的污染。本研究在高雄港區的新濱碼頭與二港口出海處，取得海水及中型毛蝦(Acetes intermedius)樣品，經前處理後，以四乙基硼化鈉進行乙基化衍生反應，正己烷萃取濃縮，以GC-FPD分析其所含有機錫種類及含量。
發現高雄港區有機錫的污染以三丁基錫(TBT)與二丁基錫(DBT)為主，海水中DBT的濃度( 98-257 ng/L )明顯大於TBT的濃度(17-133 ng/L)，毛蝦體內則是TBT的含量( 228-480 ng/g wet wt )大於DBT的含量( 97-339 ng/g wet wt )。毛蝦單位濕重TBT之含量隨著毛蝦體重增加而有減少的趨勢。2002年9月、12月與2003年3月與5月在二港口採得之毛蝦樣品體內有機錫含量無顯著季節變化，TBT的生物濃縮因子BCF介於6700-17900之間。2002年8月到2003年5月，每月在新濱碼頭採得之毛蝦樣品體內有機錫的含量隨月份亦無顯著變化，BCF值介於2200-8300之間。毛蝦累積有機錫的能力介於蚵螺與魚類之間。
而毛蝦體內有機錫的含樣隨著採樣地點的不同有顯著的差別，高雄港內毛蝦體內有機錫的含量明顯高於東港外海的毛蝦，經風險評估，東港的毛蝦有機錫含量未達到危害人體健康的程度，但高雄港內的毛蝦有機錫含量已達到可能危害人體健康的程度。
此外為探討有機錫對毛蝦的毒性，對毛蝦進行急毒性實驗。TBT對毛蝦72小時的半致死濃度(LC50)為47μg/L，隨著實驗濃度的增加
，存活毛蝦體內的TBT含量也隨之增加，其代謝產物DBT也呈相同趨勢。而DBT對毛蝦72小時LC50 為225μg/L，存活毛蝦體內DBT與其代謝產物單丁基錫(MBT)含量也會隨著DBT實驗濃度的增加而有增加有的現象。毛蝦在TBT濃度為30μg/L的海水中，累積TBT的速率為17ng/g-h，代謝的速率為8.8 ng/g-h；毛蝦在DBT濃度為100μg/L的海水中累積DBT的速率為12 ng/g-h，代謝的速率為4.2 ng/g-h。

Kaohsiung harbor is the biggest one in Taiwan. Many previous researches revealed that the pollution of organotin was usually serious in harbors. TBT contained in the antifouling paint of vessels would release into the seawater and contaminate the harbor area. In this study, shrimps (Acetes intermedius) and water samples were collected from Xinbin wharf and the second port entrance in Kaohsiung harbor. After pretreatment, ethylated with sodium tetraethylborate and extracted by hexanes, contents of organotin compounds were analyzed by GC-FPD.
The results showed that TBT and DBT were the predominant
organotin species in Kaohsiung harbor. In seawater, the concentration of DBT ( 98-257 ng/L ) was higher than TBT ( 17-133 ng/L). In shrimps, the concentration of TBT ( 228-480 ng/g ) was higher than DBT ( 98-257 ng/g). The concentration of TBT in shrimps decreased with the increased wet weight. There was no significant variation for the organotin concentrations in the shrimp samples collected from the second port entrance during the period from September 2002 to May 2003.
The bioconcentration factor (BCF) of TBT ranged between 6700-17900. The organotin concentrations in shrimps collected from Xinbin wharf also showed no significant variation from August 2002 to May 2003. The BCF values of TBT were between 2200-8300. The ability of shrimps to concentrate organotin compounds was between that of fishes and neogastropods. There were significant differences for the organotin concentrations in shrimps sampled from different sampling area. The shrimps sampled from Kaohsiung harbor were significantly higher in organotin concentration than Tungkang. According to the risk assessment, shrimps from Tungkang were much lower than the tolerable daily intake, however, the shrimps from Kaohsiung harbor were well beyond the dangerous level .
In order to understand the toxicity of organotin compounds to the shrimps, experiments on acute toxicity test were conducted. The 72-h LC50 of TBT was 47μg/L. After toxicity test, live shrimps which were exposed to organotin for 72 hours were assayed. The concentration of TBT in shrimps increased with the exposure concentrations. DBT which was the degradation product of TBT also showed the same trend. The 72-h LC50 of DBT was 225μg/L. After toxicity test period, the concentration of DBT and its metabolite MBT in shrimps also increased with the increased exposure concentrations.
The accumulation rate of the shrimps at 30μg/L TBT was 17ng/g-h and the elimination rate was 8.8 ng/g-h. The accumulation rate of the shrimps at 100μg/L DBT was 12 ng/g-h and the elimination rate was 4.2 ng/g-h.

目錄
頁次.
中文摘要…………………………………………………Ι
英文摘要…………………………………………………Ⅲ
目錄………………………………………………………Ⅴ
表目錄……………………………………………………Ⅶ
圖目錄……………………………………………………Ⅷ
壹、前言…………………………………………………1
一、有機錫化合物的種類與用途………………………1
二、有機錫化合物的特性與污染………………………4
三、有機錫化合物對生物的影響………………………12
(一)有機錫化合物對生物的毒性………………………12
(二)有機錫化合物的生化毒性機制……………………13
(三)有機錫化合物TBT的累積與代謝 …………………14
四、研究動機……………………………………………15
五、毛蝦的簡介…………………………………………17

貳、材料與方法…………………………………………19
一、藥品及溶液製備……………………………………19
二、儀器與設備…………………………………………21
三、分析方法……………………………………………22
(一)毛蝦濕重與乾重關係………………………………22
(二)毛蝦體內有機錫化合物的分析方法………………22
(三)海水中有機錫化合物的分析方法…………………23
(四)試劑水添加量的效應………………………………23
(五)四乙基硼化鈉濃度的效應…………………………24
(六)檢量線製作…………………………………………24
(七)方法偵測極限………………………………………25
(八)回收率………………………………………………26
四、實驗方法……………………………………………27
(一)田野調查……………………………………………27
(二)72小時急毒性實驗…………………………………29
(三)累積與代謝實驗……………………………………30

參、結果
一、有機錫的分析………………………………………31
(一)毛蝦濕重與乾重關係………………………………31
(二)乙基化有機錫化合物之GC-FPD分析方法層析圖…31
(三)實驗因子對有機錫的效應…………………………34
(四)檢量線的製作………………………………………37
(五)數據處理……………………………………………40
(六)方法偵測極限………………………………………41
(七)回收率………………………………………………43
二、田野調查……………………………………………45
(一)月份與季節的變化差異……………………………51
(二)地點的差異…………………………………………57
三、72小時急毒性實驗…………………………………59
(一)DBT急毒性實驗 ……………………………………59
(二)TBT急毒性實驗 ……………………………………62
四、毛蝦對有機錫累積與代謝實驗……………………65
(一) DBT累積與代謝實驗………………………………65
(二) TBT累積與代謝實驗………………………………66

肆、討論…………………………………………………67
一、實驗分析方法………………………………………67
二、田野調查……………………………………………69
(一)毛蝦體內有機錫含量與毛蝦體重的關……………69
(二)毛蝦體內有機錫含量與季節月份的關係…………69
(三)毛蝦體內有機錫含量與地點的關係………………70
(四)海水中有機錫濃度變化的探討……………………72
(五)生物濃縮因子的探討………………………………74
三、72小時毒性實驗……………………………………80
四、累積與代謝實驗……………………………………81
五、食用毛蝦的風險評估………………………………82

伍、結論…………………………………………………84
陸、參考文獻……………………………………………85

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