愛河與前鎮河皆為高雄市的主要河川，市區將近一半以上的人口分佈在沿岸，上游的工業、家庭廢水排放及農業灌溉回歸水可能直接排放至河川。此外，二河川與高雄港相接，高雄港為台灣第一大港，港內船舶往來頻繁，致使港內有機錫汙染嚴重，港內海水會隨著潮汐上溯到兩條河川中下游，可能造成河流有有機錫之汙染。
本研究在2014年對愛河與前鎮河19個測站進行四次採集水體樣本及表層沉積物，利用氣相層析配合火焰光度偵檢器進行有機錫化合物之含量分析。在愛河水樣的部分檢測到MBT含量濃度為ND-7.76 ng/L as tin，DBT為ND-10.2 ng/L as tin，TBT為ND-3.90 ng/L as tin；前鎮河中MBT為ND-2.68 ng/L as tin，DBT為ND-7.86 ng/L as tin，TBT為ND-3.22 ng/L as tin。沉積物在愛河檢測出MBT、DBT及TBT分別為ND-70.2、ND-24.6及ND ng/g as tin；在前鎮河MBT、DBT及TBT分別為ND-40.3、ND-18.4及ND ng/g as tin。所有測站採集之水樣及沉積物皆未檢測到苯基錫與辛基錫。而由兩河川水樣中與表層沉積物丁基錫含量之分佈，推測汙染源可能來自港區及河川上游，其中部分上游截流站開啟後使得有機錫含量明顯上升。2014年分成四季在愛河及前鎮河丁基錫含量之分佈趨勢觀察，當雨季時，支流上游汙染源進入主流，而導致丁基錫含量相較於非雨季高。最後，由風險商數之結果得知，具有TBT存在之測站其值介於0-0.49，顯示對環境威脅性低，仍是需要長期關注。

Love River and Chien Chen River were the main rivers of Kaohsiung. Nearly half of the population distributed in riparian areas. Industry, household wastewater and agricultural irrigation return water may flow directly to the river in the upstream. In addition, the two rivers are connected Kaohsiung harbor, a major container transshipment hub in Taiwan. However, containerships have been frequent, resulting organotin pollution in port, and contaminated water would be traced back to the downstream of river with the tide.
The purposes of this study were to understand sources of organotin pollution in Love River and Chien Chen River by analyzing samples including riverwater and surface sediments from 19 stations with GC-FPD. Result showed that concentrations of MBT, DBT and TBT in riverwater of Love River varied between ND-7.76, ND-10.2 and ND-3.90 ng/L as tin, respectively. Concentrations of MBT, DBT and TBT in riverwater of Chien Chen River varied between ND-2.68, ND-7.86 and ND-3.22 ng/L as tin, respectively. The concentrations of MBT, DBT and TBT in surface sediment of Love River varied between ND-70.2, ND-24.6 and ND ng/g as tin, respectively. The concentrations of MBT, DBT and TBT in surface sediment of Chien Chen River varied between ND-40.3, ND-18.4 and ND ng/g as tin, respectively. Seen from the results of experimental data, all samples were not detected octyltin and phenyltin. According to the distribution of butyltin of water samples and surface sediments, source of contamination probably came from the port , closure station and the upstream of river. Finally, the results of the risk quotient of TBT was between 0-0.49 found at some stations have low environmental threat, and still need a long-term concern.

摘要 i
Abstract ii
目錄 iii
表目錄 v
圖目錄 viii
壹、前言 1
一、有機錫化合物 1
(一) 有機錫化合物種類概述 1
(二) 有機錫化合物的緣起與運用情形 4
二、有機錫化合物汙染來源與環境分佈 9
三、有機錫化合物於環境中降解現象 13
四、有機錫生物毒性及對人體健康效應 15
(一) 生物毒性 15
(二) 人體健康效應 16
五、有機錫化合物的使用管制 19
六、研究動機與目標 23
(一) 愛河、前鎮河地理特性 23
(二) 研究目標 25
貳、實驗材料與方法 28
一、藥品與試藥配製 28
(一)藥品與材料 28
(二)試劑水 29
(三)試藥配置方法 29
二、儀器設備與實驗器材 30
(一) 儀器設備 30
(二) 實驗器材 30
三、樣品採集 31
(一) 採樣地點 31
(二) 採樣時間 31
(三) 採樣方法與前處理 33
四、分析方法 33
(一) 水樣中有機錫化合物之分析方法 33
(二) 沉積物中有機錫化合物之分析方法 34
(三) 檢量線製作 34
(四) 數據處理 35
(五) 方法偵測極限 38
(六) 回收率 38
(七) 主成分分析 39
叁、結果與討論 40
一、水文資料 40
(一) 水溫 40
(二) 鹽度 40
(三) 溶氧 41
(四) pH值 42
二、有機錫分析 50
(一) 層析圖譜 50
(二) 檢量線 50
(三) 方法偵測極限 50
(四) 回收率 50
三、有機錫濃度分佈 62
(一) 水樣 62
(二) 沉積物 80
四、丁基錫之吸附情形 88
五、國內外文獻比較 92
六、丁基錫環境風險評估 100
肆、結論 105
伍、參考文獻 106
附錄 114

中央氣象局 http://www.cwb.gov.tw/V7/index.htm
高雄市政府水利局 http://wrb.kcg.gov.tw/
財政部關稅總局 http://web.customs.gov.tw/mp.asp
高雄市政府民政局http://cabu.kcg.gov.tw/Report/ReportTypeFile.aspx?id=6&menuid=183高雄市環保局 http://ksenlab.ksepb.gov.tw/kh-taqm/zh-tw/b0401.aspx
行政院環保署 http://www.epa.gov.tw/np.asp?ctNode=31422&mp=epa
行政院農業委員會動植物防疫檢疫局 http://www.baphiq.gov.tw/home.php
經濟部中央地質調查所 http://hydro.moeacgs.gov.tw/011-03-explain.htm
張惠華，錫及其化合物，國家環境毒物研究中心，版次：2014年8月13日，第2.0版。
陳秀玲，李俊璋，2011，環境健康風險季刊，第一季，行政院衛生署國民健康局。
陳建中，1994 都會河川之汙染整治-蛻變中的愛河與前鎮河，國立高雄應用科技大學課程講義。
李美慧，全球化的環境汙染，科學發展，2009年，440期。
廖芳陞，與水污染相關的疾病，科學發展，2009年，438期。
蔡國維，PVC加工實務，高立出版，台北市，版次：1994年。
徐天琦，2003，有機錫對高雄港區毛蝦之毒性研究，國立中山大學海洋生物科技暨資源研究所碩士論文。
何玫儀，2004，序列相關資料的主成分分析法-以德基水庫水質監測數據為例，國立中興大學農藝學系碩士論文。
紀則賢，2004，高雄愛河水域有機錫分布之研究，國立中山大學海洋生物科技暨資源研究所碩士論文。
張貴能，2004，高雄港區有機錫分佈及其汙染史之研究，國立中山大學海洋生物科技暨資源研究所碩士論文。
李郁惠，2005，愛河及前鎮河水體中多環芳香烴含量分佈之研究，國立中山大學海洋環境及工程研究所碩士論文。
唐川禾，2007,鹿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。
何宗南 ，2008，海洋底棲多毛類Capitella sp.對底泥中有機錫的生物降解之可行性研究，國立高雄海洋科技大學海洋環境工程研究所碩士論文。
楊平，2009，高雄市愛河流域有機錫物種及其分佈之研究，國立中山大學海洋生物科技暨資源研究所碩士論文。
陳志峰，2010，港區沉積物丁基錫及多環芳香烃化河物汙染評估，國立中山大學環境工程研究所博士論文。
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。
林以淇，2013，高雄地區港口有機錫化合物分佈之研究，國立中山大學海洋生物科技暨資源研究所碩士論文。
Adeeko, A., Li, D., Forsyth, D. S., Casey, V., Cooke, G. M, Barthelemy, J., Cyr, D. G., Trasler, J. M., Robaire, B., Hales, B. F. 2003. Effects of in utero tributyltins chloride exposure in the rat on pregnancy outcome. Toxicol Sci. 74:407–415.
Alzieu, C. 1991. Environmental problems caused by TBT in France: assessment, regulations, prospects. Mar. Environ. Res. 32:7-17.
Boyer, I. J. 1989. Toxicity of dibutyltin, tributyltin and other organotin compounds to humans and to experimental animals. Toxicology. 55:253-298.
Bryan, G. W., Gibbs, P. 1991. Impact of low concentrations of tributyltin (TBT) on marine organisms: a review. In M. C. Newman, & A. W. McIntosh, Metal Ecotoxicology: Concepts and Applications, pp.323–361. Lewis Publishers, Ann Arbor.
CCME. 1999. Canadian environmental quality guidelines. Canadian Council of Ministers of the Environment, Winnipeg, Manitoba.
Champ, M. A., Seligman, P. A. 1996. “Organotin: Environmental Fate and Effects”, 1st Edition, Springer, Netherlands.
Craig, P. J. 1986. “Organometallic compounds in the environment; principles and reactions”, John Wiley and Sons, New York.
Davies, A. G., Smith, P. J. 1982. “Comprehesive Organometallic Chemistry, The Synthesis, Reactions and Structures of Organometallic Compounds, Vol. 2”. in G. Wilkinson, F. G. A Stone and E. W. Abel, p.519. Editor Pergamon Press, Oxford.
Davies, A. G. 2004. “Organotin Chemistry, 2nd, Completely Revised and Updated Edition”, Wiley-VCH.
Deelman, B. J., Koten, G.,Thoonen, S. H. L. 2004. Synthetic aspects of tetraorganotins and organotin(IV) halides. J. Organomet. Chem. 689:2145–2157.
Dowson, P. H., Bubb, J. M., Lester, J. N. 1996. Persestence and degradation pathways of tributyltin in freshwater and estuarine sediments. Estuar. Coast. Shelf Sci. 42:551- 562.
EU-Organotin Restrictions Extended to Consumer Goods. 2009. Intertek, Sparkle Vol. 454.
Evans, C. J., Karpel, S. 1985. “Organotin Compounds in Mordern Technology”, Elsevier Science Publishers, Amsterdam.
Evans, S. M., Leksono, T., McKinnell, P. D. 1995. Tributyltin pollution: A diminisihing problem following legislation limiting the use of TBT-based anti-fouling paints. Mar. Pollut. Bull., 30:14-21.
Fent, K. 1996. Ecotoxicology of organotin compounds, Cri. Rev. Toxi. 26:1-117.
Gao, J. M., Zhang, Y., Guo J. S., Jin, F., Zhang, K. 2013. Occurrence of organotins in the Yangtze River and the Jialing River in the urban section of Chongqing, China. Environ. Monit. Assess. 185:3831–3837.
Hala, D., Bristeau, S., Dagnac, T., Jobling, S. 2010. The unexpected sources of organotin contamination in aquatic toxicological laboratory studies. Aquat. Toxicol. 96:314–318.
Harino, H., Fukushima, M., Kurokawa, Y., Kawai, S. 1997. Susceptibility of bacterial populations to organotin compounds and microbial degradation of organotin compounds in environmental water. Environ Pollut.98:157-162.
Harino, H., Fukushima, M., Kurokawa, Y., Kawai, S. 1998. Degradation of the tributyltin compounds by the bacteria in water and sediment collected from harbor area of Osaka City in Japan. Environ Pollut. 98:157-162.
Hoch, M. 2001. Organotin compounds in the environment-an overview. Appl. Geochem. 16:719-743.
Huang, J. H., Matzner, E. 2004. Degradation of organotin comounds in organic and mineral forest soils. J. Plant Nutr. Soil Sci. 167:33-38.
Hua, J., Liu, S. M. 2007. Butyltin in ballast water of merchant ships. Ocean Eng. 34:1901-1907.
Kannan, K., Corsolini, S., Focardi, S., Tanabe, S., Tatsukawa, R. 1996. Accumulation pattern of butyltin compounds in dolphin, tuna, and shark collected from Italian coastal waters. Arch. Environ. Contam. Toxicol. 31:19-23.
Kannan, K., Senthilkumar, K., Giesy, J. P. 1999. Occurrence of butyltin compounds in human blood. Environ. Sci. Technol. 33:1776 -1779.
Karlsson, C. “Risk assessment of compounds that could impair the aquatic environment”, Uppsala University, Sweden.
Langston, W. J., Pope, N. D. 1995. Determinants of TBT adsorption and desorption in estuarine sediments. Mar. Pollut. Bull. 31:32-43.
Lee, R. F., Valkirs, A. O., Seligman, P. F. 1989. Importance of microalgae in the biodegradation of tributyltin inestuarine waters. Environ. Sci. Technol. 29:154-60.
Leung, H.W., Minh, T.B., Murphy, M.B., Lam, J.C.W., So, M.K., Martin, M., Lam, P.K.S., Richardson, B.J. 2012. Distribution, fate and risk assessment of antibiotics in sewage treatment plants in Hong Kong, South China. Environ. Int. 42:1-9.
Liu,A., Gonzalez, R.D. 1999. Adsorption/desorption in a system consisting of humic acid,heavy metals, and clay minerals. J. Colloid. Interface Sci. 218:225-232
Maguire, R. J., Carey, J. H., Hale, E. J. 1983. Degradation of tri-n-butyltin species in water. J.Agric. Food Chem. 31:1060-1065.
Maguire, R. J., Tkacz, R. J. 1985. Degradation of the tri-n-butyltin species in water and sediment from Toronto Harbor. J. Agric. Food Chem. 33:947-953.
Martin-Landa, L., Pablos, F. D., Marr, L.L. 1989. Determination of organotins in fish and sediments by gas chromatography with flame photometric detection. Anal. Proc. 26:16-29.
McAllister, B. G, Kime, D. E. 2003. Early life exposure to environmental levels of the aromatase inhibitor tributyltin causes masculinisation and irreversible sperm damage in zebrafish (Danio rerio). Aquat. Toxicol.65:309-316.
Murai, R., Sugimoto, A., Tanabe, S, Takeuchi, I. 2008. Biomagnification profiles of tributyltin (TBT) and triphenyltin (TPT) in Japanese coastal food webs elucidated by stable nitrogen isotope ratios. Chemosphere. 73:1749-1756.
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.
Omae, I. 2003. Organotin antifouling paints and their alternatives. Appl. Organometal. Chem. 17:81-105.
Raffle, P. A. B., Lee, W. R., McCallum, R. I., Murray, R. 1987. Hunter's Diseases of Occupations. 7th Edition, Little Brown, 310-311, Boston.
Roni , M. J. J., Masod, A. Z. 1996. The metabolism of testosterone by the periwinkle (Littorina zittorea) in vitro and in viva: effects of Tributyltin. Mar. Environ. Res. 42: 161–166.
Rochow, E. G., Abel, E. W. 1975. “The Chemistry of Germanium, Tin and Lead.” 2nd Edition, John Wiley & Sons, Now York.
Schwarzenbach, R., Berg, M., Arnold, C. G., Muller S. R., Muhlemann, J. 2001. Sorption and desorption behavior of organotin compounds in sediment-pore water systems. Environ. Sci. Technol. 35:3151-3157.
Schaefer, C. H., Miura, T., Dupras, Jr. E. F., Wilder, W. H. 1981. Environmental impact of the fungicide triphenyltin hydroxide after application to rice fields. J. Econ. Entomol. 74:597–600.
Schramel, P., Samsahl, K., Pavlu, J. 1973. Some determinations of Hg, As, Se, Sb, Sn and Br in water plants, sediments and fishes in Bavarian rivers. Int. J. Environ. Stud., 5:37-40.
Sun, H., Huang, G., Dai, S. 1996. Adsoption behavior and QSPR studies of organotin compounds on estuarine sediment. Chemosphere. 33:831-838.
Titley-O'Neal, C. P., Munkittrick, K. R., MacDonald, B. A.. 2011. The effects of organotin on female gastropods. J. Environ. Monitor. 13:2360-2388.
Tsang, C. K., Lau, P. S., Tam, N. F. Y., Wong, Y. S. 1999. Biodegradation capacity of tributyltin by two Chlorella species. Environ. Pollut. 105:289-297.
Uhle, M. E.,Chin, Y. P.,Aiken, G. R., Mcknight, D. M. 1999. Binding of polychlorinated biphenyls to aquatic humic substances: the role of substrate and sobate propterties on partitioning. Environ. Sci. Technol. 33:2715-2718.
Valkirs, A. O., Seligman, P. F., Stang, P. M., Homer, V. 1986. Measurement of butyltin compounds in San-Diego Bay. Mar Pollut Bull. 17:319-324.
Van der Kerk G. J. M. 1975. Present status of the use of organotin compounds. Chem. Ztg. 99:66-32.
Van der Kerk G. J. M., Luitjen J. G. A. 1954. The biocidal properties of organotin compounds. Appl. Chem. 4:314-319.
Yamabe, Y., 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.
Yi , A. X. L., Leung, K. M. Y., Lam, M. H. W., Lee, J. S., Giesy, J. P. 2012. Review of measured concentrations of triphenyltin compounds in marine ecosystems and meta -analysis of their risks to humans and the environment. Chemosphere. 89:1015-1025.
Zhang, K. G., Shi, J. B., He, B., Xu, W. H., Li, X. D., Jiang, G. B. 2013. Organotin compounds in surface sediments from selected fishing ports along the Chinese coast. Chinese. Sci. Bull. 58:231-237.