本研究係採集高雄地區十八個港口，共計21個採樣點之乾、溼季水樣及表層沉積物，利用氣相層析配合火焰光度偵測器(GC-FPD)分析有機錫化合物之含量，以瞭解各港口有機錫汙染情況及探討汙染來源。各港口有機錫化合物濃度分佈以丁基錫化合物為主，水樣中單丁基錫濃度介於6.5~86.1 ng/L as tin，二丁基錫濃度介於4.1~24.8 ng/L as tin，三丁基錫濃度介於2.8~96.8 ng/L as tin，總丁基錫濃度介於27.4~146 ng/L as tin；表層沉積物中單丁基錫濃度介於6.8~413 ng/g as tin，二丁基錫濃度介於5.3~129 ng/g as tin，三丁基錫濃度介於2.5~56.2 ng/g as tin，總丁基錫濃度介於15.2~584 ng/g as tin，各測站皆無檢測出苯基錫化合物。本研究有機錫化合物濃度明顯低於其他國家大型港口，而高雄港與過去研究相比，有機錫化合物濃度十年來已經明顯下降，由此可知在有關當局的嚴格控管之下有一定成效。但研究結果發現，部分漁港有機錫化合物的汙染較高雄港區來的嚴重，顯示區域型漁港在有機錫化合物方面的控管還有很大的努力空間。

Samples of seawaters and surface sediments were collected from eighteen harbors in Kaohsiung, with twenty-one sampling sites. The objectives of this study were to understand organotin pollution of those harbors and to investigate the sources of organotin as analyzed by gas chromatography-flame photometric detection(GC-FPD). The results showed that butyltins were the major components of organotin pollution of the harbors. The concentrations of MBT, DBT, TBT and ΣBT in seawaters varied between 6.5~86.1 ng/L as tin, 4.1~24.8 ng/L as tin, 2.8~96.8 ng/L as tin and 27.4~146 ng/L as tin. The concentrations of MBT, DBT, TBT and ΣBT in surface sediments varied between 6.8~413 ng/g as tin, 5.3~129 ng/g as tin, 2.5~56.2 ng/g as tin and 15.2~584 ng/g as tin. Phenyltin was not detected in any harbor. The levels of organotin compounds observed in this study were lower than most of the reported values from other foreign harbors. In comparison with the previous studies in Kaohsiung Harbor, organotin concentrations have dropped significantly. The improvements are attributed to the effective control over the utilization of organotin compounds by the authorities. However, organotin pollution of some fishing harbors were much serious than that of Kaohsiung Harbor. Our government agency should pay more attention on their fishing harbors.

論文審定書 i
致謝 ii
摘要 iii
Abstract iv
目錄 v
表目錄 vii
圖目錄 viii
壹、前言 1
一、有機錫化合物之特性 1
二、有機錫化合物之用途及使用情形 1
三、有機錫化合物汙染來源與環境流佈 2
四、有機錫化合物之沉降、降解、生物累積 3
五、生物與人體之暴露途徑及毒性影響 4
六、世界各國與國內對有機錫化合物之管制情形 4
七、研究目的 5
貳、實驗材料與方法 19
一、藥品與試藥配製 19
(一) 藥品與材料 19
(二) 試劑水 21
(三) 試藥配製方法 21
二、儀器設備與實驗器材 22
(一) 儀器設備 22
(二) 實驗器材 23
三、樣品採集 24
(一) 採樣地點 24
(二) 採樣時間 24
(三) 採樣方法與前處理 24
四、分析方法 25
(一) 水樣中有機錫化合物之分析方法 25
(二) 沉積物中有機錫化合物之分析方法 25
(三) 檢量線製作 26
(四) 方法偵測極限 26
(五) 回收率 27
參、結果與討論 34
一、水文資料 34
(一) 水溫 34
(二) 溶氧 34
(三) pH值 34
(四) 鹽度 35
二、有機錫分析 36
(一) 層析圖譜 36
(二) 檢量線製作 36
(三) 數據處理 36
(四) 方法偵測極限 37
(五) 回收率 37
三、各測站有機錫分析結果 38
(一) 水樣部分 38
(二) 沉積物部分 43
(三) TBT之吸附情形 45
四、國內外相關文獻比較 46
肆、結論 85
伍、參考文獻 86
陸、附錄 90
一、水樣分析方法 90
二、沉積物分析方法 91

Berg, M., Arnold, C. G., Muller, S. R., Muhlemann, J., Schwarzenbach, R. P. (2001). Sorption and desorption behavior of organotin compounds in sediment-pore water systems. Environ. Sci. Technol., 35: 3151-3157.
Chen, C. F., Kao, C. M., Dong, C. D., Chen, C. W. (2010). Butyltin contamination in sediments and seawater from Kaohsiung Harbor, Taiwan. Environ. Monit. Assess., 169: 75-87.
Craig, P. J. (1986). Organometallic compounds in the environment-principles and reactions. John Wiley and Sons.
De Oliveira, C. R., Dos Santos, D., Madureira, L. A., De Marchi, M. R. (2010). Speciation of butyltin derivatives in surface sediments of three southern Brazilian harbors. J. Hazard. Mater., 181: 851-856.
Diez, S., Abalos, M., Bayona, J. M. (2002). Organotin contamination in sediments from the Western Mediterranean enclosures following 10 years of TBT regulation. Water Res., 36: 905-918.
Diez, S., Lacorte, S., Viana, P., Barcelo, D., Bayona, J. M. (2005). Survey of organotin compounds in rivers and coastal environments in Portugal 1999-2000. Environ. Pollut., 136: 525-536.
Edward, R. K., Alfred, W. J., Michael, L. K. (1989). Acute toxicity of triphenyltin hydroxide to three cladoceran species. Environ. Pollut., 56: 11-17.
European, C. (2007). Impact assessment of potential restrictions on the marketing and use of certain organotin compounds. European Commission. Directorate-General Enterprise and Industry.
Evans, C. J., Karpel, S. (1985). Organotin compounds in modem technology. Organomet. Chem. Libr., 16: 178–217.
Fent, K. (1996). Ecotoxicology of organotin compounds. Crit. Rev. Toxicol., 26: 3-117.
Gerald, E. W., Leslie, L. M., Emile, M. L., Michael, K. L., Christine, H. D. (1985). Effects of organotins on growth and survival of two marine diatoms, Skeletonema costatum and Thalassiosira pseudonana. Chemosphere, 14: 383-392.
Hoch, M. (2001). Organotin compounds in the environment — an overview. Appl. Geochem., 16: 719-743.
Horiguchi, T., Li, Z., Uno, S., Shimizu, M., Shiraishi, H., Morita, M., Thompson, J. A. J., Levings, C. D. (2003). Contamination of organotin compounds and imposex in molluscs from Vancouver, Canada. Mar. Env. Res., 57: 75-88.
Hua, J., Liu, S. M. (2007). Butyltin in ballast water of merchant ships. Ocean Eng., 34: 1901-1907.
Lee, C. C., Hsieh, C. Y., Tien, C. J. (2006). Factors influencing organotin distribution in different marine environmental compartments, and their potential health risk. Chemosphere, 65: 547-559.
Liu, L. L., Chen, S. J., Peng, W. Y., Hung, J. J. (1997). Organotin concentrations in three intertidal neogastropods from the coastal waters of Taiwan. Environ. Pollut., 98: 113-118.
Michel, P., Averty, B., Andral, B., Chiffoleau, J. F., Calgani, F. (2001). Tributyltin along the coasts of Corsica (Western Mediterranean): A persistent problem. Mar. Pollut. Bull., 42: 1128-1132.
Milivojevič Nemanič, T., Milačič, R. , Ščančar, J. (2008). A survey of organotin compounds in the Northern Adriatic Sea. Water, Air, and Soil Pollution, 196: 211-224.
Nemanic, T. M., Leskovsek, H., Horvat, M., Vriser, B., Bolje, A. (2002). Organotin compounds in the marine environment of the Bay of Piran, Northern Adriatic Sea. J. Environ. Monit., 4: 426-430.
Oecd (2001). Report on the test results of endocrine disrupting effects of tributyltin (TBT) on fish (Draft). 1-32.
Omae, I. (2003). Organotin antifouling paints and their alternatives. Appl. Organomet. Chem., 17: 81-105.
Rüdel, H., Lepper, P., Steinhanses, J. (2003). Retrospective monitoring of organotin compounds in marine biota from 1985 to 1999:Results from the German Environmental Specimen Bank. Environ. Sci. Technol., 37: 1731–1738.
Robert, J. H., Michael, A. U., Peter, F. S., Aldis, O. V. (1992). ES&T series: The marine biocide tributyltin. Assessing and managing the environmental risks. Environ. Sci. Technol., 26: 232-237.
Rodriguez-Gonzalez, P., Encinar, J.R., Alonso, J.I.G., Sanz-Medel, A. (2002). Determination of butyltin compounds in coastal sea-water samples using isotope dilution GC-ICP-MS. J. Anal. At. Spectrom., 17: 824-830.
Scancar, J., Zuliani, T., Turk, T., Milacic, R. (2007). Organotin compounds and selected metals in the marine environment of Northern Adriatic Sea. Environ. Monit. Assess., 127: 271-82.
Segovia-Martinez, L., Bouzas-Blanco, A., Campins-Falco, P., Seco-Torrecillas, A. (2010). Improving detection limits for organotin compounds in several matrix water samples by derivatization-headspace-solid-phase microextraction and GC-MS. Talanta, 80: 1888-93.
Shim, W. J., Hong, S. H., Kim, N. S., Yim, U. H., Li, D., Oh, J. R. (2005). Assessment of butyl- and phenyltin pollution in the coastal environment of Korea using mussels and oysters. Mar. Pollut. Bull., 51: 922-931.
Stebbing, A. R. D. (1985). Organotins and water quality. Some lessons to be learned. Mar. Pollut. Bull., 16: 383-390.
Sun, H., Huang, G., Dal, S. (1996). Adsorption behaviour and QSPR studies of organotin compounds on estuarine sediment. Chemosphere, 33: 831-838.
Tang, C.-H. , Wang, W.-H. (2008). Butyltin accumulation in two marine bivalves along a pollution gradient. Environmental Toxicology and Chemistry, 27: 2179-2185.
Thoonen, S. H. L., Deelman, B. J., Van Koten, G. (2004). Synthetic aspects of tetraorganotins and organotin(IV) halides. J. Organomet. Chem., 689: 2145-2157.
Veges, M., Rodríguez-González, P., García Alonso, J. I., Sanz-Medel, A., Fodor, P. (2007). Isotope dilution analysis mass spectrometry for the routine measurement of butyltin compounds in marine environmental and biological samples. Microchem. J., 85: 115-121.
Whalen, M. M., Loganathan, B. G., Kannan, K. (1999). Immunotoxicity of environmentally relevant concentrations of butyltins on human natural killer cells in vitro. Environ. Res. , 81: 108-116.
Yamabe, Y., Hoshino, A., Imura, N., Suzuki, T., Himeno, S. (2000). Enhancement of androgen-dependent transcription and cell proliferation by tributyltin and triphenyltin in human prostate cancer cells. Toxicol. Appl. Pharmacol. , 169: 177-184.
Zhang, K. G., Shi, J. B., He, B., Xu, W. H. Li, X. D., Jiang, G. B. (2012). Organotin compounds in surface sediments from selected fishing ports along the Chinese coast. Chinese Science Bulletin, 58: 231-237.
Zuo, Z., Chen, S., Wu, T., Zhang, J., Su, Y., Chen, Y., Wang, C. (2011). Tributyltin causes obesity and hepatic steatosis in male mice. Environ. Toxicol., 26: 79-85.
行政院環保署.
Http://www.Epa.Gov.Tw.
行政院環境保護署毒物資料庫. Http://www.Epa.Gov.Tw/ch/sitepath.Aspx?Busin=324&path=1702&list=1702.
財政部關稅總局.
Http://web.Customs.Gov.Tw/statistic/statistic/yerstatistic.Asp.
高雄市政府海洋局.
Http://doe.Godsmt.Com.Tw/data/monitor_5/monitor_5.Aspx.
國立海洋科技博物館籌備處.
Http://ship.Nmmst.Gov.Tw/ship/content/139.
張貴能 (2004). 高雄港區有基錫之分佈研究. 國立中山大學海洋生物科技暨資源研究所碩士論文.
李麗婷 (2011). 高雄愛河及前鎮河有機錫化合物之分佈. 國立中山大學海洋生物科技暨資源研究所碩士論文.
盧毓婷 (2012). 屏東縣漁港有機錫分佈之研究. 國立中山大學海洋生物科技暨資源研究所碩士論文.