臺灣博碩士論文加值系統

本研究主要針對自來水之消毒副產物-鹵化乙酸 (haloacetic acid; HAA) 作鑑定分析；自來水中消毒副產物以一氯乙酸（monochloroacetic acid; MCAA）、二氯乙酸 (dichloroacetic acid; DCAA)、三氯乙酸 (trichloroacetic acid; TCAA)、一溴乙酸 (monobromoacetic acid; MBAA)及二溴乙酸 (dibromoacetic acid; DBAA)為主，因此本研究以此五種化合物作為目標化合物。目標化合物分別以US EPA Method 552.1、552.2及APHA Method 6251B方法分析，所得目標化合物之校正曲線關係均達到0.995以上，其中以執行US EPA Method 552.2之所得結果表現較佳。執行US EPA Method 552.2、US EPA Method 552.1及APHA Method 6251B所得方法偵測極限分別為0.086~0.470 ng/mL、0.083~1.833 ng/mL及0.161~0.827 ng/mL。利用US EPA Method 552.2方法分析台灣區之自來水，結果顯示台灣各城市之自來水中HAAs含量皆在美國第一階段法規限值 ( 60 ng/mL ) 之安全範圍之內。為了發展新的分析方法，以2-aminophenol與HAAs進行衍生化反應，所得到的產物經純化後，以氣相層析質譜儀分析鑑定，確認得到主要產物為chloromethylbenzoxazole、bromomethylbenzoxazole、dichloromethyl- benzoxazole、 dibromomethylbenzoxazole及trichloromethyl- benzoxazole等五種methylbenzoxazole衍生物；而形成具有芳香性之雙環結構，對於HAAs衍生成具有螢光性質之化合物，具有正面指標之意義。

The objective of this study is to appraise and analyze of haloacetic acids (HAAs) in tap water. Haloacetic acids, which include monochloroacetic acid (MCAA), dichloroacetic acid (DCAA), trichloroacetic acid (TCAA), monobromoacetic acid (MBAA), and dibromoacetic acid (DBAA), are major constituents of so-call disinfection by-products. The five HAAs mentioned above were analyzed by various methods to compare the suitability of the methods. All three methods, USEPA Method 552.1, USEPA Method 552.2, and APHA Method 6251B, tested were able to produce calibration curves for five targeted HAAs with correlation coefficients of 0.995 or higher. The USEPA Method 552.2 consistently provided a better result than that of others’. The ranges of method detection limit for USEPA Method 552.1, USEPA Method 552.2, and APHA Method 6251B are 0.083-1.833 ng/mL, 0.086-0.470 ng/mL, and 0.161-0.827 ng/mL, respectively. This indicates that the HAA concentrations in the tap water are all lower than the limit regulated by the Stage 1 D/DBP Rules. Furthermore, this study attempted to develop a new method for HAAs analysis using fluorescent compound derivation scheme. The method generates HAAs derivatives with 2-aminophenol. After purification, the resulting compounds are chloromethylbenzoxazole, dichloro- methylbenzoxazole, trichloromethylbenzoxazole, bromomethyl- benzoxazole, and dibromomethylbenzoxazole. These derivatives were successfully analyzed with GC/MS. Additionally, the aromatic structure of these compounds should possess a fluorescent characteristic that can be measured by fluorescence related methods. Further research on the utilization of this property for analysis should be warranted.

目 錄 I
圖目錄 V
表目錄 VII
中文摘要 VIII
英文摘要 IX
一、 前言 1
二、 文獻整理 3
1. 影響鹵化乙酸產生的原因 3
1.1. 加氯量及水中藻類含量之影響 3
1.2. 腐植酸含量之影響 4
1.3. pH與總有機鹵素之影響 4
1.4. 添加抑制劑的影響 4
1.5. 溴離子之影響 5
1.6. 水溫之影響 6
1.7. 反應時間之影響 6
2. 分析方法現況 7
2.1. 液-液萃取-酸性甲醇衍生-氣相層析儀/電子捕捉檢測器分析 7
2.2. 固相萃取技術 - 酸性甲醇衍生-氣相層析儀/電子捕捉檢測器分析 7
2.3. 酸性甲醇衍生-固相微萃取-以氣相層析質譜儀分析 8
2.4. 微量液-液萃取法-重氮甲烷衍生-氣相層析儀/電子捕捉檢測器分析 8
2.5. Pentafluorobenzyl bromide ( PFBBr ) 衍生-氣相層析質譜儀分析 9
2.6. IC/UV檢測 9
3. 有機酸衍生化試驗 10
三、 實驗材料與方法 11
1. 材料與設備 11
2. 試劑與標準品 12
3. 取樣與樣品的保存 14
3.1. 樣品瓶的準備 14
3.2. 取樣 15
3.3. 樣品的保存 15
4. 實驗方法 15
4.1. 固相萃取膜法/酸性甲醇衍生法－US EPA Method 552.1 15
4.2. 液-液萃取法/酸性甲醇衍生法－US EPA Method 552.2 17
4.3. 液-液萃取/重氮甲烷甲酯化 18
4.4. 定量方式 19
4.5. 儀器分析條件 20
5. 方法偵測極限之測定 21
5.1. 預估方法偵測極限 21
5.2. 方法偵測極限之確認 22
6. 品管樣品分析 22
7. 台灣區自來水中HAAS含量調查 23
8. HAAS衍生化試驗 23
8.1. 衍生物之純化 24
8.2. 衍生物之確認 27
四、 結果與討論 28
1. 不同方法分析所得檢量線之線性 28
1.1. US EPA Method 552.1 28
1.2. US EPA Method 552.2 28
1.3. APHA Method 6251B 29
2. 方法偵測極限 30
3. US EPA METHOD 552.2分析真實樣品 30
3.1. 台灣各城市自來水中HAAs之含量 30
3.2. 品管樣品分析 31
4. HAAS之衍生化研究 31
4.1. Chloromethylbenzoxazole衍生物之確認 31
4.2. Bromomethylbenzoxazole衍生物之確認 31
4.3. Dichloromethylbenzoxazole衍生物之確認 32
4.4. Dibromomethylbenzoxazole衍生物之確認 32
4.5. Trichloromethylbenzoxazole衍生物之確認 32
五、 結論 34
1. HAAS分析部分 34
2. HAAS衍生化部分 34
六、 參考資料 36
圖目錄
圖 1、三氯乙酸與Pentafluorobenzyl bromide 之反應 40
圖 2、固相萃取膜萃取濃縮裝置 41
圖 3、重氮甲烷產生器 42
圖 4、有機酸形成imidazole之反應 43
圖 5、2,3-二氨基苯與有機酸酯之合環副反應 43
圖 6、鹵化乙酸之衍生化反應 44
圖 7、氣相層析儀/電子捕捉檢測器分析HAAs之層析圖 45
圖 8、利用US EPA Method 552.1方法分析MCAA之校正曲線 46
圖 9、利用US EPA Method 552.1方法分析DCAA之校正曲線 47
圖 10、利用US EPA Method 552.1方法分析MBAA之校正曲線 48
圖 11、利用US EPA Method 552.1方法分析TCAA之校正曲線 49
圖 12、利用US EPA Method 552.1方法分析DBAA之校正曲線 50
圖 13、利用US EPA Method 552.2方法分析MCAA之校正曲線 51
圖 14、利用US EPA Method 552.2方法分析DCAA之校正曲線 52
圖 15、利用US EPA Method 552.2方法分析MBAA之校正曲線 53
圖 16、利用US EPA Method 552.2方法分析TCAA之校正曲線 54
圖 17、利用US EPA Method 552.2方法分析DBAA之校正曲線 55
圖 18 、利用APHA Method 6251B方法分析MCAA之校正曲線 56
圖 19、利用APHA Method 6251B方法分析MBAA之校正曲線 57
圖 20、利用APHA Method 6251B方法分析DCAA之校正曲線 58
圖 21、利用APHA Method 6251B方法分析TCAA之校正曲線 59
圖 22、利用APHA Method 6251B方法分析DBAA之校正曲線 60
圖 23、台北市自來水中之HAAs層析圖 61
圖 24、雲林自來水中之HAAs層析圖 62
圖 25、中壢自來水中之HAAs層析圖 63
圖 26、宜蘭自來水中之HAAs層析圖 64
圖 27、彰化自來水中之HAAs層析圖 65
圖 28、苗栗自來水中之HAAs層析圖 66
圖 29、台南自來水中之HAAs層析圖 67
圖 30、高雄自來水中之HAAs層析圖 68
圖 31、台灣不同城市自來水中總鹵化乙酸（total HAA）含量 69
圖 32、chloromethylbenzoxazole之氣相層析質譜層析圖 70
圖 33、bromomethylbenzoxazole之氣相層析質譜層析圖 72
圖 34、dichloromethylbenzoxazole之氣相層析質譜層析圖 73
圖 35、dibromomethylbenzoxazole之氣相層析質譜層析圖 74
圖 36、trichloromethylbenzoxazole之氣相層析質譜層析圖 75
圖 37、chloromethylbenzoxazole之質譜圖 77
圖 38、bromomethylbenzoxazole之質譜圖 77
圖 39、dichloromethylbenzoxazole之質譜圖 78
圖 40、dibromomethylbenzoxazole之質譜圖 79
圖 41、trichloromethylbenzoxazole之質譜圖 80
表目錄
表 1、HAAs的分子式及沸點 81
表 2、不同方法校正曲線之配製濃度 (ng/mL) 82
表 3、以不同方法分析HAAs校正曲線線性比較 83
表 4、不同方法分析HAAs所得之方法偵測極限(ng/mL) 84
表 5、台灣不同城市自來水中鹵化乙酸含量 85
表 6、品管樣品分析結果 87
表 7、氯與溴化合物同位素波峰之強度（分子離子比例關係） 88

行政院環保署環境檢驗所，2000，水中鹵乙酸檢測方法─固相萃取濃縮/氣相層析儀/電子捕捉偵測器法 ( NIEA W533.50B )。
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