高雄港為臺灣最大的國際商港，除了是臺灣主要貨櫃轉運的樞紐港外，也是南部主要貨物的進出口港埠。港內貨櫃船往來頻繁，並且有數個造、修船廠及漁港，因此港內有機錫汙染嚴重，而愛河、前鎮河河口位於高雄港內，港內之汙染水源會隨著潮汐上溯至兩河川；上游河段之家庭、工業廢水之排放及農業灌溉回歸水，亦可能造成河流有機錫之汙染。
本研究係採集愛河、前鎮河共計19個測站之乾、雨季漲退潮水樣及表層沉積物，利用氣相層析配合火焰光度偵測器進行分析有機錫化合物之含量，以監測愛河、前鎮河有機錫汙染之情況及瞭解有機錫之汙染源。
愛河、前鎮河各測站有機錫化合物濃度分布，以單丁基錫及二丁基錫汙染為主，愛河水樣中單丁基錫（MBT）、二丁基錫（DBT）及三丁基錫（TBT）含量分別為13.4-43.6 、2.6-9.9、ND-13.5 ng/L as tin，前鎮河水樣中MBT、DBT及TBT含量依序為3.1-28.1、2.1-10.9、ND-9.1 ng/L as tin；愛河表層沉積物中MBT、DBT及TBT含量分別為20.6-92.3、7.6-26.2、ND-15.4 ng/g as tin，前鎮河表層沉積物中MBT、DBT及TBT含量分別為22.4-70.0、6.4-14.1、ND-31.9 ng/g as tin。
兩河川水樣中之有機錫化合物之分布與表層沉積物呈現了一致性，各測站皆無檢測出苯基錫汙染，可能是農業活動減少或禁用三苯醋錫之關係所致；愛河及前鎮河除了在靠近河口之下游河段有機錫汙染嚴重外，在上游河段及截流站之廢水汙染較嚴重，使得呈現另一汙染高峰。

Kaohsiung Harbor is the largest international sea port in Taiwan, a lot of ships around the world pass in and out frequently, the pollution of organotin is very serious in the harbor area. Love River and Chien-Chen River may be polluted by the seawater tidal action from the Kaohsiung harbor. Domestic, industrial and agricultural wastewaters discharged into the upstream sections may also cause the pollution of organotin.
The purposes of this study were to understand sources of organotin pollution by analying the content of organotin compounds and to monitor the organotin pollution of the rivers in Kaohsiung. Samples including surface sediments and riverwaters were collected from nineteen stations of Love River and Chien-Chen River. The results revealed that concentrations of MBT, DBT and TBT in the riverwaters of Love River varied between 13.4-43.6, 2.6-9.9 and ND-13.5 ng/L as tin. The concentrations of MBT, DBT and TBT in the riverwaters of Chien-Chen River were 3.1-28.1, 2.1-10.9 and ND-9.1 ng/L as tin, respectively. The concentrations of MBT, DBT and TBT in the surface sediments of Love River varied between 20.6-92.3, 7.6-26.2 and ND-15.4 ng/g as tin. The concentrations of MBT, DBT and TBT in the surface sediments of Chien-Chen River were in the range of 22.4-70.0, 6.4-14.1, ND-31.9 ng/g as tin, respectively. MBT and DBT were detected in all the samples of all the sampling stations of Love River and Chien-Chen River.
Distribution of organotin compounds in riverwaters and surface sediments showed a consistency between these two rivers. No phenyltin pollution was detected at all stations, probably due to the decline in agricultural activities and the ban on utilizing triphenyltin acetate as pesticide. Except the highest organotin pollution appeared in the outfall of Love River and Chien-Chen River, other high values of pollution were found near the upper reaches of both rivers.

中文摘要 i
英文摘要 ii
目錄 iii
表目錄 v
圖目錄 vi
壹、前言 1
一、有機錫化合物理化特性、用途與使用情形 1
(一)有機錫化合物之理化特性 1
(二)有機錫化合物之用途與使用情形 1
二、有機錫化合物汙染來源與環境分布 3
(一) 有機錫化合物之汙染來源 3
(二) 有機錫化合物之環境流布 4
三、有機錫暴露途徑、生態毒性及對人體健康效應 4
(一)生物暴露途徑與生態毒性 4
(二)人體暴露途徑與毒性 5
四、世界各國對有機錫之管制情形 5
五、研究動機 6
(一)地理文化特性 6
貳、材料與方法 9
一、藥品與溶液製備 9
(一)藥品部分 9
(二)試劑水 9
(三)試藥配製 10
二、儀器設備與實驗器材 10
三、樣品採集與前處理 11
(一)採樣地點 11
(二)採樣時間 11
(三)採樣方法與樣品前處理 12
四、分析方法 13
(一)水樣中有機錫化合物的分析方法 13
(二)沉積物中有機錫化合物的分析方法 13
(三) 檢量線製作 13
(四)方法偵測極限 14
(五)回收率 14
参、結果與討論 16
一、水文資料 16
二、有機錫分析 19
三、有機錫濃度分布結果 20
（一）水樣部分 20
（二）表層沉積物 24
肆、結論 26
伍、參考文獻 27
附錄、原始數值 70

 
表目錄
表1-1、有機錫化合物之物理、化學特性 31
表1-2、歐盟國家於2002年和2007年有機錫之銷售量及用途 32
表1-3、有機錫化合物之主要用途 33
表1-4、氧化三丁錫及氫氧化三苯錫之許可用途 34
表1-5、台灣地區近年來進口有機錫化合物數量表 35
表1-6、環境中有機錫化合物之汙染來源 36
表1-7、不同種類的有機錫化合物主要影響之生物物種 37
表2-1、執行有機錫分析之GC-FPD操作條件 38
表3-1、愛河乾季滿潮水文資料表 39
表3-2、愛河乾季乾潮水文資料表 40
表3-3、愛河雨季滿潮水文資料表 41
表3-4、愛河雨季乾潮水文資料表 42
表3-5、前鎮河乾季滿潮水文資料表 43
表3-6、前鎮河乾季乾潮水文資料表 43
表3-7、前鎮河雨季滿潮水文資料表 44
表3-8、前鎮河雨季乾潮水文資料表 44
表3-9、金屬錫原子量及各種氯化有機錫分子量 45
表3-10、有機錫化合物分析方法偵測極限 45
表3-11、有機錫添加回收率試驗結果 46
表3-12、國內外水樣相關文獻之比較 47
表3-13、國內外沉積物相關文獻之比較 47

 
圖目錄
圖1-1、丁基錫與苯基錫之基本結構圖 48
圖1-2、氯化三丁基錫與氯化三苯基錫的分解過程 48
圖1-3、有機錫於食物鏈中之傳輸與對不同營養階層之暴露途徑 49圖1-4、人體接觸有機錫化合物之可能途徑 50
圖1-5、高雄市列管水汙染源家數、行業別分布圖 51
圖2-1、本研究愛河、前鎮河採樣地點 52
圖2-2、水樣中有機錫化合物之分析方法流程圖 53
圖2-3、沉積物中有機錫化合物之分析方法流程圖 54
圖3-1、乙基化有機錫化合物之 GC-FPD層析圖譜 55
圖3-2、分析水樣中丁基錫化合物之檢量線 56
圖3-3、分析水樣中苯基錫化合物之檢量線 57
圖3-4、分析沉積物中丁基錫化合物之檢量線 58圖3-5、分析沉積物中苯基錫化合物之檢量線 59
圖3-6、愛河乾季（a）漲潮（b）乾潮 水樣有機錫濃度分布圖 60
圖3-7、愛河雨季（a）漲潮（b）乾潮 水樣有機錫濃度分布圖 61
圖3-8、高雄市36~98年各區人口數統計圖 62
圖3-9、愛河乾季（a）漲潮（b）乾潮水樣總丁基錫濃度分布圖 63
圖3-10、愛河雨季（a）漲潮（b）乾潮水樣總丁基錫濃度分布圖 64
圖3-11、前鎮河乾季（a）漲潮（b）乾潮 水樣有機錫濃度分布圖 65
圖3-12、前鎮河雨季（a）漲潮（b）乾潮 水樣有機錫濃度分布圖 66
圖3-13、前鎮河乾季（a）漲潮（b）乾潮 水樣總丁基錫濃度分布圖 67
圖3-14、前鎮河雨季（a）漲潮（b）乾潮 水樣總丁基錫濃度分布圖 68
圖3-15、愛河表層沉積物中有機錫濃度分布圖 69
圖3-16、前鎮河表層沉積物中有機錫濃度分布圖 69

1. 中央氣象局 http://www.cwb.gov.tw/V7/index.htm
2. 財政部關稅總局http://web.customs.gov.tw/statistic/statistic/yerstatistic.asp
3. 高雄市政府工務局下水道工程處，2008年愛河至平橋至鼎新橋流域水質水文監測季水質改善委託技術服務案之調查報告。
4. 唐川禾，2007，耳門溪及四草漁港環境及生物體中有機錫之研究，國立中山大學海洋生物科技暨資源研究所博士論文。
5. 徐天琦，2003，有機錫對高雄港區毛蝦之毒性研究，國立中山大學海洋資源研究所碩士論文。
6. 張貴能，2004，高雄港區有機錫分佈及其污染史之研究，國立中山大學海洋資源研究所碩士論文。
7. 李郁惠，2005。愛河及前鎮河水體中多環芳香烴含量分布之研究，國立中山大學海洋環境及工程研究所碩士論文。
8. 蔡致維，2004，愛河之水文，國立中山大學海洋資源研究所碩士論文。
9. 莊玉妃，2006，殖場有機錫污染程度與來源研究調查，國立成功大學環境醫學研究所碩士論文。
10. 行政院環保署，2008，毒性化學物管理執行方案規畫與公告列管評析計劃。
11. Alzieu C., Sanjuan J., Deltreil J.P. and Borel M. 1986. Tin Contaimination in Arcachon Bay : Effects on Oyster Shell Anomalies. Mar. Poll. Bull. 17:494–498.
12. Alzieu, C. 1986. The detrimental effects on oyster culture in France–Evolution since antifouling paint regulation. In: Proceedings of the organotin symposium of the oceans 86 conference. pp. 1130-1134.
13. Alzieu, C., 1991. Environmental problems caused by TBT in France: assessment, regulations, prospects. Mar. Environ. Res. 32: 7–17.
14. Bancon-Montigny, Ch., Lespes, G. and Potin-Gautier, M., 2004. Organotin survey in the Adour-Garonne basin. Water Res. 38:933-946
15. Berto, D., Giani, M., Boscolo, R., Covelli, S.,Giovanardi, O., Massironi, M. and Grassia, L. 2007. Organotin (TBTand DBT) in water, sediments, and gastropods of the southern Venice lagoon (Italy). Mar. Pollut. Bull. 55:425-435.
16. Blaber, Check, 1970. The occurrence of a penis-like outgrowth behind the right tentacle in spent females of Nucella lapillus (L.). Proceedings of the Malacological Society of London 39:231–233.
17. Craig, P. J. 1986. Organometallic Compounds in the Environment–Principles and Reaction, John Wiley & Sons, New York.
18. Diez, S.,Abalos, M. and Bayona, J. M. 2002. Organotin contamination in sediments from the western Mediterranean enclosures following 10 years of TBT regulation. Water Res. 36:905-918
19. Evans, C. J. and S. Karpel. 1985. Organotin Compounds in Modern Technology, Elsevier Science Publishers, Amsterdam.
20. Evans, C.J., Karpel, S. 1985. Organotin compounds in modem technology. J. Organomet. Chem. Libr. 16:178–217.
21. Fent, K. 1996. Ecotoxicology of Organotin Compounds, Cri. Rev. Toxi. 26 :1–117.
22. Fent, K. and Hunn, J. 1995. Organotins in freshwater harbors and rivers: Temporal distribution, annual trends and fate. Environ. Toxicol. Chem. 14:1123-1132.
23. Gomez-Ariza, J.L., Morales, E., Giraldez, I., 1998. Spatial distribution of butyltin and phentyltin compounds on the Huelva coast (southwest Spain). Chemosphere. 37:937–950.
24. Hoch, M. 2001. Organotin Compounds in the Environment–an Overview. Appl. Geochem. 16:719–743.
25. Horiguchi, T., H. Shiraishi., M. Shimizu and M. Morita. 1994. Imposex and Organotin Compounds in Thais Clavigera and T. Bronni in Japan. J. Mar. Biol. Ass. UK 74:651–669.
26. Huaa, J. and Liu, S. M. 2007. Butyltin in ballast water of merchant ships. Ocean. Eng. 34:1901-1907.
27. Huggett, R. J., P. F. Seligman and A. O. Valkirs. 1992. The Marine Biocide Tributyltin–Assessing and Managing the Environmental Risks. Environ. Sci. Technol. 26:232–237.
28. Jarvinen, A. W., Tanner, D. K., Kline, E. R. and Knuth, M. L., 1988. Acute and chronic toxicity of triphenyltin hydroxide to fathead minnow (pimephales promelas) following brief or continuous exposure. Environ. Pollut. 52:289-301.
29. Lee, R. F. 1991. Metabolism of Tributyltin by Marine Animals and Possible Linkages to Effects. Mar. Environ. Res. 32:29–35.
30. Lee, C.C, Hsieh,C.Y, Tien, and C.J. 2006. Factors influencing organotin distribution in different marine environmental compartments, and their potential health risk. Chemosphere. 65:547-59.
31. Maguire, R.J. 1985. Organotin compounds in the aquatic environment: scientific criteria for assessing their effects on environmental quality. National Research Council Canada. pp. 284.
32. Matthiessen P, Gibbs PE. 1998. Critical appraisal of the evidence for tributyltin-mediated endocrine disruption in molluscs. Environ Toxicol Chem. 17:37–43.
33. Nwaogu, T. A., Zarogiannis, P., Tuffnell, N., Floyd, P. 2007. Impact Assessment of Potential Restrictions on the Marketing and Use of Certain Organotin Compounds. European Commission irectorate-General Enterprise and Industry, UK.
34. Quevauviller, Ph., Bruchet, A. and Donard, O. F. X. 1991. Leaching of organotin compounds from poly(vinyl chloride) (PVC) material. Appl. Organometal. Chem. 5:125-129.
35. Shim, W. J.,Oh, J. R., Kahng, S. H., Shim, J. H. and Lee, S. H. 1999. Horizontal distribution of butyltins in surface sediments from an enclosed bay system, Korea. Environ. Pollut. 106:351-357.
36. Smith, B.S. 1971. Sexuality in the American mud snail, Nassarius obsoletus say.Proceedings of the Malacological Society of London. 39:377–378.
37. Sun, H., Huang, G. and Dai, S. 1996. Adsorption behavior and studies of organotin compounds on Estuarine sediment. Chemosphere. 33:831-838.
38. Stebbing, A. R. D. 1985. Organotin and Water Quality-Some Lessons to Be Learned, Mar. Poll. Bull. 16:383-390.
39. Sun, H., G. Huang and S. Dai. 1996. Adsorption Behavior and Studies of Organotin Compounds on Estuarine Sediment. Chemosphere. 33:831–838.
40. Schramel P, Samsahl K, Pavlu J. 1973. Some determination of He, As, Se, Sb, Sn and Br in water plants, sediments and fishes in Bavarian rivers. International Journal of Environmental Analytical Chemistry. 5: 37-40.
41. Valkirs, A. O., P. F. Seligman, P. M. Stang and V. Homer. 1986. Measurement of Butyltin Compounds in San–Diego Bay, Mar. Poll. ull. 17:319–324.
42. van der Kerk GJM. 1975. Present status of the use of organotin compounds. Chem. Ztg. 99: 26-32
43. van der KerK GMJ, Luitjen JGA. 1954. The biocidal properties of organotin compounds. Applied Chemistry. 4: 314-319.
44. Walsh, G.E., McLaughlan, L.L., Louie, M. K. and Deans, C. H. 1985. Effect of organotins on growth and survival of two marine diatoms, skeletonema costatum and thalassira pseudonana. Chemosphere. 14:383-392.
45. Whalen, M. M., Logamathan, B. G. and Kannan, K. 1999. Immunotoxivity of environmentally relevant concentration of butyltin on human nayural killer cells in Virto. Environ. Res. 81:108-116.
46. Yamabe, Y. and Hoshino, A. 2000. Enhancement of angrogen-dependent transcription and cell proliferation by tributyltin and triphenyltin in human prostate cancer cell. Toxic. App. Pharm. 169:177-184.