本研究針對高屏溪流域，包括里嶺大橋、河濱公園、高屏大橋、萬大支流及高屏河口等五個測站，分別採集四季的水樣和表層沉積物等二種樣本，利用氣相層析火焰光度偵測器(GC-FPD)分析有機錫化合物之含量，以瞭解高屏溪流域有機錫化合物汙染分佈狀況。各測站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ND~33.9 ng/L as tin，二丁基錫濃度介於ND~3.2 ng/L as tin，三丁基錫濃度介於ND~1.4 ng/L as tin，總丁基錫濃度介於ND~33.9 ng/L as tin；表層沉積物中單丁基錫濃度介於14.9~30.8 ng/g as tin，二丁基錫濃度介於ND~6.6 ng/g as tin，三丁基錫濃度則均無驗出，總丁基錫濃度介於14.9~30.9 ng/g as tin，各測站皆無檢測出辛基錫及苯基錫化合物。本研究有機錫化合物濃度明顯低於其它國家河流，而與國內其它河流相比較，有機錫化合物濃度也明顯低於其它河流。最後，由風險商數(RQ)評估水生環境風險，各測站有機錫化合物之RQ值除里嶺大橋(S1測站)於秋季時為0.18外，其餘均小於0.1，表示其環境風險是微小可忽略的。

The main goal of this study is monitoring of the species and the concentration distribution of organotin compounds in the Gaoping River Basin. Water and sediment samples were collected from five sampling stations, including Li-Ling bridge, Riverside park, Gaoping bridge, Wan-Da tributary and Gaoping estuary on March, June, October and December, 2014. Gas chromatography-flame photometric detection(GC-FPD) was used to analyze organotin compounds in samples. The results showed that butyltins were the major components of organotin pollution of the sampling sites. The concentrations of MBT, DBT, TBT and ΣBT in freshwater varied between ND~33.9 ng/L as tin, ND~3.2 ng/L as tin, ND~1.4 ng/L as tin and ND~33.9 ng/L as tin. The concentrations of MBT, DBT, TBT and ΣBT in surface sediments varied between 14.9~30.8 ng/g as tin, ND~6.6 ng/g as tin, ND ng/g as tin and 14.9~30.9 ng/g as tin. Octyltins and phenyltins were not detected in any sampling sites. The levels of organotin compounds observed in this study were lower than most of the reported values from other domestic and foreign rivers. Finally, the environmental risk posed by the organotin in aquatic ecosystems of Gaoping River Basin was assessed through calculation of the risk quotient(RQ). The highest RQ values of 0.18 was observed at Li-Ling bridge in October 2014. All the other RQ values are less than 0.1 that is of insignificant environmental risk.

目 錄
國立中山大學研究生學位論文審定書 i
摘要 ii
Abstract iii
目 錄 iv
表目錄 vi
圖目錄 vii
壹、 前言 1
一、有機錫化合物之種類及特性 1
二、有機錫化合物之用途及使用情形 3
三、有機錫化合物之汙染來源與環境影響 7
四、有機錫化合物在環境中的降解現象 10
五、有機錫化合物對生物與人體之暴露途徑及毒性 10
六、有機錫化合物於世界各國與國內之管制情形 16
七、高屏溪流域簡介 18
八、研究目的 18
貳、實驗材料與方法 22
一、藥品與試藥配製 22
(一) 藥品與材料 22
(二) 試藥配製方法 23
二、儀器設備與實驗器材 24
(一) 儀器設備 24
(二) 實驗器材 25
三、樣品採集 25
(一) 採樣地點 25
(二) 採樣時間 30
(三) 採樣方法與前處理 30
四、分析方法 31
(一) 水樣中有機錫化合物之分析方法 31
(二) 沉積物中有機錫化合物之分析方法 33
(三) 檢量線製作 33
(四) 方法偵測極限 36
(五) 回收率 36
(六) 風險評估 37
參、結果與討論 38
一、水文資料 38
(一) 水溫 38
(二) 溶氧 38
(三) pH值 40
(四) 鹽度 40
二、有機錫分析 41
(一) 層析圖譜 41
(二) 檢量線製作 41
(三) 數據處理 41
(四) 方法偵測極限 53
(五) 回收率 53
三、各測站有機錫分析結果 55
(一) 水樣部分 55
(二) 表層沉積物部分 58
(三) 丁基錫之環境分佈情形 70
四、國內外相關文獻比較 72
五、丁基錫之環境風險評估 77
肆、結論 79
伍、參考文獻 80


表目錄
表1-1 有機錫化合物的物理、化學特性表 2
表1-2 有機錫化合物的主要用途 5
表1-3 臺灣地區近年來進口有機錫化合物的數量表(單位：公斤) 6
表1-4 環境中有機錫化合物的汙染來源 11
表1-5 不同種類的有機錫化合物主要影響之生物物種 14
表1-6 TBT對水中生物之影響 14
表1-7 有機錫化合物之許可用途與禁止運作事項 17
表1-8 高屏溪流域各鄉鎮市一覽表 21
表2-1　有機錫化合物分析之GC-FPD操作條件 34
表3-1 各測站水文資料表 39
表3-2　金屬錫原子量及各種氯化有機錫分子量 52
表3-3　有機錫化合物分析方法偵測極限 54
表3-4　有機錫化合物添加回收率(％)試驗結果 54
表3-5 春季各測站水樣丁基錫化合物濃度(ng/L as tin) 56
表3-6 夏季各測站水樣丁基錫化合物濃度(ng/L as tin) 56
表3-7 秋季各測站水樣丁基錫化合物濃度(ng/L as tin) 59
表3-8 冬季各測站水樣丁基錫化合物濃度(ng/L as tin) 59
表3-9 春季各測站表層沉積物丁基錫化合物濃度(ng/g as tin) 64
表3-10 夏季各測站表層沉積物丁基錫化合物濃度(ng/g as tin) 64
表3-11 秋季各測站表層沉積物丁基錫化合物濃度(ng/g as tin) 66
表3-12 冬季各測站表層沉積物丁基錫化合物濃度(ng/g as tin) 66
表3-13 各測站MBT之分配係數 71
表3-14 國內外關於水樣中丁基錫化合物含量之相關文獻比較(ng/L as tin) 73
表3-15 國內外關於沉積物中丁基錫化合物含量之相關文獻比較(ng/g as tin) 76
表3-16 各測站丁基錫之RQ指數 78


圖目錄
圖1-1　丁基錫、辛基錫與苯基錫化合物之基本結構 4
圖1-2　有機錫化合物進入環境的主要途徑及其降解之示意圖 8
圖1-3　三丁基錫自船舶防塗料中溶出的作用機制 9
圖1-4　三有機錫化合物在環境中的降解過程 12
圖1-5　人體曝露有機錫化合物之可能途徑 15
圖1-6 高屏溪流域位置圖 20
圖2-1 本研究採樣地點位置圖 26
圖2-2 (S1)里嶺大橋 27
圖2-3 (T1)河濱公園 27
圖2-4 (S2)高屏大橋 28
圖2-5 (T2)萬大支流 28
圖2-6 (S3)高屏河口 29
圖2-7　水樣中有機錫化合物之分析方法流程圖 32
圖2-8　沉積物中有機錫化合物之分析方法流程圖 35
圖3-1 乙基化有機錫化合物之GC-FPD層析圖譜 42
圖3-2　分析淡水中丁基錫化合物之檢量線。(a) MBT (b) DBT (c) TBT 43
圖3-3　分析淡水中辛基錫化合物之檢量線。(a) MOcT (b) DOcT 44
圖3-4　分析淡水中苯基錫化合物之檢量線。(a) MPT (b) DPT (c) TPT 45
圖3-5　分析海水中丁基錫化合物之檢量線。(a) MBT (b) DBT (c) TBT 46
圖3-6　分析海水中辛基錫化合物之檢量線。(a) MOcT (b) DOcT 47
圖3-7　分析海水中苯基錫化合物之檢量線。(a) MPT (b) DPT (c) TPT 48
圖3-8　分析表層沉積物中丁基錫化合物之檢量線。(a) MBT (b) DBT (c) TBT49
圖3-9　分析表層沉積物中辛基錫化合物之檢量線。(a) MOcT (b) DOcT 50
圖3-10 分析表層沉積物中苯基錫化合物之檢量線。(a) MPT (b) DPT (c) TPT 51
圖3-11 各測站水樣中丁基錫化合物濃度(ng/L as tin)季節變化圖 60
圖3-12 各測站水樣中總丁基錫(ΣBTs)濃度(ng/L as tin)季節變化圖 61
圖3-13 各測站水樣中三種丁基錫化合物含量相對百分比季節變化圖 62
圖3-14 各測站表層沉積物中丁基錫化合物濃度(ng/g as tin)季節變化圖 67
圖3-15 各測站表層沉積物中總丁基錫(ΣBTs)濃度(ng/g as tin)季節變化圖 68
圖3-16 各測站表層沉積物中三種丁基錫化合物含量相對百分比季節變化圖 69

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