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研究生:張貴能
研究生(外文):Guei-neng Jang
論文名稱:高雄港區有機錫之分佈及其污染史之研究
論文名稱(外文):The organotin distribution and pollution history in Kaohsuing Harbor areas
指導教授:王維賢
指導教授(外文):Wei-Hsien Wang
學位類別:碩士
校院名稱:國立中山大學
系所名稱:海洋資源學系研究所
學門:自然科學學門
學類:海洋科學學類
論文種類:學術論文
論文出版年:2004
畢業學年度:92
語文別:中文
論文頁數:78
中文關鍵詞:有機錫沉積物高雄港
外文關鍵詞:Kaohsiungorganotinsediment
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高雄港為台灣第一大港及世界第四大港,世界各地貨櫃船往來頻繁,且港內有數個造船廠、修船場和漁港,因此港內有機錫污染應當十分嚴重,此外高雄港同時有愛河及前鎮河注入,此可能為高雄港區有機錫污染的第二來源。本研究採集高雄港內海水及沉積物進行有機錫分析,來了解高雄港區有機錫的污染分佈情況。
高雄港區海水中三丁基錫(TBT)的濃度介於170~480 ng/L,二丁基錫(DBT)介於150~400 ng/L,單丁基錫(MBT) 介於80~283 ng/L。海水中TBT污染最嚴重的地區為工作船渠及駁二碼頭(第三船渠),其濃度都大於350 ng/L;海水中DBT和MBT濃度最高的地區亦為工作船渠,但在河口地區DBT和MBT的濃度則高於其他停船處,其原因可能為河川上游的都市廢水(愛河)及工業廢水(前鎮河)所帶來的污染。
高雄港區沉積物中TBT含量最高的區域為工作船渠,其中TBT平均含量為25.3 mg/kg,為前鎮漁港的4.5倍及駁二碼頭的5.3倍,而此三區TBT平均含量已超過對二枚貝及端腳類之10-d LC50(分別為2.6 mg/kg及2.1 mg/kg);DBT和MBT含量最高的地區亦為工作船渠,平均含量分別為12.4 mg/kg及9.7 mg/kg。在河口地區沉積物中三種丁基錫含量皆不超過1.2 mg/kg,因此在河口地區有機錫之污染並不嚴重。
在有機錫的組成上工作船渠、駁二碼頭及前鎮漁港皆以TBT為主,約佔50%以上,但隨沉積物深度呈遞減的趨勢,而DBT和MBT的百分比隨沉積物深度則呈遞增的趨勢,此表示TBT在沉積物中會逐漸地降解為DBT和MBT;但在河口地區TBT%隨深度遞減的趨勢並不明顯,其原因可能為DBT和MBT除了由TBT降解而來外,DBT和MBT也會從工業廢水和都市廢水中而來。
參考國外相關文獻發現高雄港沉積物中有機錫之含量確實比其他大型港口(如巴塞隆納和大阪港)高出許多;就小區域的比較,前鎮漁港有機錫之含量也高於香港及德國的遊艇港,因此高雄港區沉積物中有機錫之污染算是相當嚴重。
The Port of Kaohsiung is the biggest harbor in Taiwan and also the fourth largest harbor in the world. There are several shipyards and fishing ports in the Port of Kaohsiung, therefore, the pollution of organotin should be very serious in the harbor area. In addition, there are Love River and Chien-Chen River pouring into the Port of Kaohsiung. This may be the second source of organotin pollution of the harbour of Kaohsiung. Seawater and sediment samples in the harbor of Kaohsiung were gathered in this research. Analysis on organotin contents were conducted to understand the distribution of the organictin in the Port of Kaohsiung.
In seawater, the concentration of tributyltin (TBT) is between 170~480 ng/L, the concentration of dibutyltin (DBT) is between 150~400 ng/L and the concentration of monobutyltin (MBT) is between 80~283 ng/L. Working Duck and The Third Duck are among the serious areas of TBT pollution where the concentrations of TBT in seawater are over 350 ng/L. Concentrations of DBT and MBT are also the highest at the Working Duck. In the estuary areas, the concentrations of DBT and MBT are higher than TBT. It is probably due to the input of domestic sewage (Love River) and industrial wastewater (Chien-Chen River) which may bring extra DBT and MBT into the estuary areas.
The highest TBT concentration in sediment is observed at Working Duck with average value of 25.3 mg/kg. This concentration is 4.5 times higher than that of Chien-Chen Fishing Port and 5.3 times higher than that of The Third Duck. All the concentrations of these three areas are over 10-d LC50 to bivalve (2.6 mg/kg) and amphipoda (2.1 mg/kg). The highest DBT and MBT concentrations are also observed in sediment of Working Duck, and the average concentration of DBT is 12.4 mg/kg and MBT is 9.7 mg/kg. In the estuary areas the concentration of organotins are lower than 1.2 mg/kg, therefore, the pollution of organotins is lesser serious in the estuary areas than the other sampling areas in Kaohsiung Harbor.
The composition of organotins is mainly TBT in Working Duck, The Third Duck and Chien-Chen Fishing Port, and TBT accounts for more than 50%. TBT percentage decreases with sediment depth, however DBT and MBT percentage increases with sediment depth. It shows that TBT will be degraded for DBT and MBT gradually in the sediment. The trend that TBT percentage decreases with the sediment depth is not obvious in the estuary area, and the probable reason is that the source of DBT and MBT is not only from TBT degrading, but also from the input of city sewage and industry wastewater.
According to this study, the content of organotins in sediment in the Port of Kaohsiung is indeed higher than other large-scale harbor (Barcelona and Port of Osaka). By comparing smaller areas, the content of organotins in Chien-Chen Fishing Port is also higher than marina of Hong Kong and German. It is concluded that the pollution of organotins in the Port of Kaohsiung is very serious in comparison with most other areas in the world.
謝誌……………………………………………………….………………….…Ι
中文摘要…………………………………………………………………….…II
英文摘要………………………………………….……..……………………IV
目錄………………………………………………...……………....………...ⅤI
表目錄……………………………………………………………….……...VIII
圖目錄………………………………………………….…………………..…IX
第一章 前言……...……………………………………………………….….1
一、有機錫化合物之用途……………………………………………………..1
二、有機錫化合物進入環境之途徑………………………………………..…3
三、有機錫化合物之降解、生物累積及沉降………….……………………..6
四、有機錫化合物之毒性……………………………….……………………..8
五、有機錫化合物之使用限制………………………………………...……...11
六、研究目的……………………………………………..……………………11

第二章 材料與方法……………………………………………………..….13
一、藥品及試劑…….…………………………………………………………13
二、試劑配製……………………….………………………………………....14
三、儀器及器材….……………………………………………………………15
四、採樣方法………….………………………………………………………15
五、分析方法………………………………………………………………….17
1. 沉積物粒徑分析…………………………...………………………….17
2. 沉積物中有機錫之分析方法………...…………………………….…17
3. 水體中有機錫之分析方法………………………...………………….18
4. 氣相層析之條件……...…………………………………………….…18
5. 沉積物中有機質之分析………………...………………………..…...19
6. 沉積物之定年…………………………………………...…..………...20
六、有機錫分析之品管部分…………………………………………………21
1. 格林鈉試劑中有機錫化合物之含量……...………………………….21
2. 去除沉積物中硫化物之干擾測試………...……………………….…21
3. 沉積物分析方法之檢量線………………………...………………….22
4. 海水分析方法之檢量線……...…………………………………….…22
5. 沉積物方法偵測極限…………………...………………………..…...22
6. 海水方法偵測極限……………………………………...…..………...23
7. 回收率…………………………………………………………………23

第三章 結果與討論………………………………………………...………24
一、有機錫之分析…………………………………………………….….…...24
1. 實驗方法部份……………………………………………...………….24
2. 品管部分………….……………………………………………….…..27
二、海水中有機錫之濃度………………………………………………….…35
三、沉積物之粒徑分佈與有機錫之含量………….…………………………37
1. 粒徑大小隨深度之變化…………………………………...………….37
2. 不同粒徑中有機錫之含量………….…………………………….…..39
四、各測站有機質之含量及其吸附TBT之情形……………………………43
五、沉積物之定年結果………….……………………………………………49
六、近期有機錫之污染………….……………………………………………53
七、沉積物中有機錫含量隨深度之變化……………………….……………57
八、各有機錫百分比隨沉積物深度之變化….………………………………63
九、與國外文獻比較………………………….………………………………71

第四章 總結………………………………………………………………73
第五章 參考文獻………………………………………………………….75
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