自來水廠淨水程序中添加含氯消毒劑，具有淨化水質與確保水質安全衛生之功用。但消毒劑與存在於水中之天然或人為有機物發生反應會生成消毒副產物(Disinfection By-Products，DBPs)，其中以鹵化乙酸（Haloacetic Acids，HAAs）與三鹵甲烷（Trihalomethanes，THMs）為消毒副產物之主要組成物種。
本研究針對南部三大淨水廠（A、B、C三廠）進行消毒副產物鹵化乙酸與三鹵甲烷之分析，探討三水廠使用高級淨水程序淨化與降低消毒副產物之生成濃度情形，並藉此調查目前南部地區自來水中鹵化乙酸與三鹵甲烷的濃度分布情形，其中A、B兩廠使用UF/RO系統，C廠使用BAC系統。鹵化乙酸之分析方法係根據美國環保署公告之Method 552.3進行實驗，三鹵甲烷的部分則是使用頂空固相微萃取法（HS-SPME）進行實驗，亦同步分析溶解性有機碳（DOC）與其他水質檢測項目，討論各檢測項目與消毒副產物之生成是否具有相關性，以作為法規訂定參考依據與提供台灣地區自來水廠在淨水程序中操作之參考。
本研究在民國96年6月至民國97年4月分別進行南部三水廠之採樣分析，南部三水廠最終清水的九種鹵化乙酸（HAA9）之總濃度分布如下：A廠為28.71 ± 14.77μg/L，B廠為 24.43 ± 15.70μg/L，C廠為28.91 ± 14.38μg/L，三水廠皆符合美國環保署現行HAA5＝60μg/L的標準。而最終清水的三鹵甲烷（THMs）之總濃度分布如下：A廠為9.99 ± 3.39μg/L，B廠為 8.49 ± 4.05μg/L，C廠為0.94 ± 2.12μg/L，三水廠皆符合我國環保署現行規定THMs＝80μg/L的標準。且結果顯示南部地區HAA9組成物種主要是BCAA，其次為TCAA，而THMs主要組成物種則為三氯甲烷（CHCl3）。
另外，在本研究中發現DBPs與其他水質檢測項目之相關性，是以DOC値與溫度變化對DBPs濃度較有相關性，其中在DOC値方面，是以原水之DBPs之生成潛勢與DOC之相關性較佳；而溫度與DBPs濃度相關程度雖然較差，但仍隨溫度上升DBPs濃度亦有上升之趨勢。總結本研究之結果，A、B水廠使用之高級淨水程序（UF/RO系統）對於DBPs最終生成濃度能有效降低，相較於使用BAC系統之C廠有較佳的出水水質，對於南部地區自來水之淨化能有效提升出水水質，但由於南部地區含溴之鹵化乙酸物種濃度偏高，故建議對此現象需加以改善與控制。

Disinfectants, such as chlorine, are widely used in water treatment plants to ensure the safety and quality of drinking water. However, these disinfectants easily react with some natural or man-made organic compounds in raw water and then form disinfection by-products (DBPs). For example, halogenated acetic acid (HAAs) and trihalomethanes (THMs) are two main components of DBPs.
The purposes of this study are to analyze the concentration of DBPs including HAAs and THMs in drinking water and investigate the distribution of DBPs in the processes of three advanced water treatment plants in southern Taiwan. The analytical method of HAAs is based on the USEPA Method 552.3 and THMs is analyzed by headspace solid-phase microextraction(HS-SPME). Moreover, some factors which may influence the formation of DBPs such as dissolved organic carbon (DOC) and water temperature are also analyzed to further discuss the relation to the generation of DBPs. Through this study, the results could be the reference for operation control in water treatment plants and regulation setting in Taiwan.
The samples of drinking water were collected in three advanced water treatment plants in southern Taiwan from June 2007 to April 2008. The analyzed HAA9 results were 28.71 ± 14.77μ g / L in Plant A, 24.43 ± 15.70 μ g / L in Plant B, 28.91 ± 14.38 μ g / L in Plant C. Comparing the HAA5 results with the maximum contaminant level (MCL) in USEPA, it was clearly found that all the values were under the standard of 60 μ g / L. As to THMs, the results were 9.99 ± 3.39μ g / L in Plant A, 0.94 ± 2.12 μ g / L in Plant B, 28.91 ± 14.38 μ g / L in Plant C and greatly under the EPA standard of 80 μ g / L in Taiwan. Furthermore, the major species of HAA9 in order were BCAA and TCAA while THMs was trichloromethane (CHCl3).
In the relation between DOC and DBPs, the results demonstrated that DOC was more relative to DBPs in raw water; meanwhile, the water temperature did not show great relation. In general, despite the poor correlation, it was still could conclude that the concentration of DBPs increases with the increase of DOC and temperature.
In conclusion, the research results showed that the removal efficiency of DBPs in Plant A and B (UF/RO system) is greater than Plant C (Biological Activated Carbon system, BAC system ), and all three advanced water treatment plants could show greatly effectiveness in drinking water quality improvement. However, higher concentration of bromine products in HAAs was discovered in this research. It was suggested that the phenomenon should be further discussed and controlled.

謝誌 ………...…Ⅰ

中文摘要……………………………………………………….………Ⅲ

英文摘要………………………………………………................ Ⅴ

目錄…………………………………………………………………Ⅶ

表目錄………………………………………………………………XII

圖目錄……………………………………………………………XIII


第一章 前言.………………………………………………………....1-1
1.1 研究緣起 ...............1-1
1.2 研究目的 ………1-2

第二章 文獻回顧……………………………………………………....2-1
2.1 水中有機物之來源與影響…………………………………….…2-1
2.2 消毒副產物…………..………….………………………………..2-4
2.3 含氯消毒副產物………………………………………..………...2-5
2.4鹵化乙酸與鹵化乙酸生成潛勢…………………………………2-10
2.4.1 鹵化乙酸之分類…………………………………………...2-10
2.4.2鹵化乙酸之來源……………………………………..….. 2-12
2.4.3鹵化乙酸之生成因素…….………………………………...2-12
2.4.4 鹵化乙酸之危害性質……………………………………...2-16
2.4.5鹵化乙酸之法規管制標準…………………………..….. 2-18
2.4.6鹵化乙酸之生成潛勢…….………………………………...2-19

2.5三鹵甲烷與三鹵甲烷生成潛勢………………………………...2-20
2.5.1 三鹵甲烷之分類…………………………………………...2-20
2.5.2三鹵甲烷之來源……………………………………..….. 2-21
2.5.3三鹵甲烷之生成因素…….………………………………...2-22
2.5.4 三鹵甲烷之危害性質……………………………………...2-26
2.5.5三鹵甲烷之法規管制標準…………………………..….. 2-27
2.5.6三鹵甲烷之生成潛勢…….………………………………...2-28

第三章 研究方法…………………………………………….……….3-1
3.1鹵化乙酸（Haloacetic acids, HAA5）…………………….………....3-1
3.1.1 分析藥品.…………………………………………………....3-2
3.1.2 分析儀器及設備..……………………………………………3-3
3.1.3 採樣及保存..………………………….………………….....3-3
3.1.4 HAAs分析步驟..………………………….…………………3-4
3.1.5 氣相層析儀分析條件..………………………….…………...3-6
3.1.6 檢量線之建立..……………..…………….…………………3-6

3.2三鹵甲烷（Trihalomethane, THMS）…………………….………....3-7
3.2.1 分析藥品.…………………………………………………....3-7
3.2.2 分析儀器及設備..……………………………………………3-7
3.2.3 採樣及保存..………………………….………………….....3-8
3.2.4 THMS分析步驟..………………………….…………………3-9
3.2.5 氣相層析儀分析條件..………………………….…………...3-9
3.2.6 檢量線之建立..……………..…………….………………...3-10

3.3消毒副產物生成潛勢（DBPs formation potential, DBPFP）…3-10
3.3.1鹵化乙酸生成潛勢（HAA formation potential, HAAFP）.….3-11
3.3.2三鹵甲烷生成潛勢（THM formation potential, THMFP）…3-11
3.3.3非揮發性溶解性有機碳（Non-Purgable Dissolved Organic
Carbon, NPDOC）..…………….………….………………...3-12

3.4 本研究樣本採集.………………………………………………...3-13

第四章 結果與討論……...…………………………………………………...4-1
4.1 三水廠水質分析結果…..……………………………………………..4-1
4.1.1原水來源不同之DBPs 濃度分布情形……………………...4-2
4.1.2淨水程序不同之DBPs 濃度分布情形………………..…….4-5

4.2鹵化乙酸之濃度分析……………………………………..…..…...4-9
4.2.1各淨水廠處理程序中鹵化乙酸之生成差異………………...4-9
4.2.2鹵化乙酸濃度之季節性差異…………………………..….4-19

4.3三鹵甲烷之濃度分析……………………………………..……...4-23
4.3.1各淨水廠處理程序中三鹵甲烷之生成差異…………….....4-23
4.3.2三鹵甲烷濃度之季節性差異…………………………..…...4-28

4.4消毒副產物與DOC之關係……………………..……….……...4-31

4.5消毒副產物與溫度之關係……………………….……….……...4-41

4.6消毒副產物與pH之關係……………………….……….……...4-50


第五章 結論及建議…………………………………………………..5-1
5-1 結論……………………………………………………………….5-1
5-2 建議……………………………………………………………….5-4

參考文獻……………………………………………………………...…..….參-1
附錄A 品保品管數據…………..…………………………………….A-1

表目錄

表2.1 NOM組成物種…………………………….………………2-3
表2.2加氯消毒副產物種類……………………………..…………2-7
表2.3鹵化乙酸化合物之物理性質……………………..…………2-10
表2.4各國HAA單一物種之法規值比較………….……………2-19
表2.5三鹵甲烷化合物之物理性質……….………………………2-20
表2.6國內外飲用水三鹵甲烷之管制值…………………………2-27
表3.1 A淨水廠之採樣明細………………………….…...............3-14
表3.2 B淨水廠之採樣明細………………………….…...............3-15
表3.3 C淨水廠之採樣明細………………………….…...............3-16

圖目錄
圖1.1 研究架構圖…………………….………………………………1-3
圖2.1鹵化乙酸之結構式……………………………..…..…...……2-11
圖2.2三鹵甲烷之結構式…….…………………………………..…2-21
圖3.1 HAAs之實驗分析步驟……..…………………….....………3-7
圖3.2 THMs之實驗分析步驟……..……………………...………3-12
圖3.3 A淨水廠之處理流程圖…….….....………………………3-17
圖3.4 B淨水廠之處理流程圖…….….....………………………3-18
圖3.5 C淨水廠之處理流程圖…….….....………………………3-19
圖4.1四分位等級圖…….….....……………………..…………….4-2
圖4.2 A、B廠原水與清水HAA5四分位等級圖………………4-3
圖4.3 A、B廠原水與清水HAA9四分位等級圖…….……...…4-4
圖4.4 A、B廠原水與清水THMs四分位等級圖………………4-5
圖4.5 B、C廠原水與清水HAA5四分位等級圖…….……...…4-6
圖4.6 B、C廠原水與清水HAA9四分位等級圖………………4-7
圖4.7 B、C廠原水與清水THMs四分位等級圖…….……...…4-8
圖4.8 A淨水廠HAA5物種組成…………………………..……4-12
圖4.9 A淨水廠HAA9物種組成…….………………...…...…4-12
圖4.10 B淨水廠HAA5物種組成………………………………4-15
圖4.11 B淨水廠HAA9物種組成…….………………....…...…4-15
圖4.12 C淨水廠HAA5物種組成………………………………4-18
圖4.13 C淨水廠HAA9物種組成…….………………....…...…4-18
圖4.14三淨水廠月均溫之變化…….………………..…....…...…4-21
圖4.15 A、B廠HAA9之季節性差異…………………………4-21
圖4.16 A、B廠HAA9之季節性差異………………....…...…4-22
圖4.17 A淨水廠THMs物種組成…….………………....…...…4-24
圖4.18 B淨水廠THMs物種組成………………………………4-26
圖4.19 C淨水廠THMs物種組成…….………………....…...…4-27
圖4.20 A、B廠THMs之季節性差異…………………………4-30
圖4.21 B、C廠THMs之季節性差異………………....…...…4-30
圖4.22 DOC與DBPs生成之關係（A水廠原水）…………4-35
圖4.23 DOC與DBPs生成之關係（B水廠原水）…………4-36
圖4.24 DOC與DBPs生成之關係（C水廠原水）…………4-37
圖4.25 DOC與DBPs生成之關係（A水廠清水）…………4-38
圖4.26 DOC與DBPs生成之關係（B水廠清水）…………4-39
圖4.27 DOC與DBPs生成之關係（C水廠清水）…………4-40
圖4.28 DOC與Temp生成之關係（A水廠原水）…………4-44
圖4.29 DOC與Temp生成之關係（B水廠原水）…………4-45
圖4.30 DOC與Temp生成之關係（C水廠原水）…………4-46
圖4.31 DOC與Temp生成之關係（A水廠清水）…………4-47
圖4.32 DOC與Temp生成之關係（B水廠清水）…………4-48
圖4.33 DOC與Temp生成之關係（C水廠清水）…………4-49
圖4.34 DOC與pH生成之關係（A水廠原水）……………4-52
圖4.35 DOC與pH生成之關係（B水廠原水）……………4-53
圖4.36 DOC與pH生成之關係（C水廠原水）……………4-54
圖4.37 DOC與pH生成之關係（A水廠清水）……………4-55
圖4.38 DOC與pH生成之關係（B水廠清水）……………4-56
圖4.39 DOC與pH生成之關係（C水廠清水）……………4-57

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