臺灣博碩士論文加值系統

本研究利用化學分析與螢光測試法(Microtox)檢測台灣2009板新水廠、豐原水廠、福興水廠與鳳山水廠之枯水期與豐水期原水與清水消毒副產物 (三鹵甲烷、鹵乙酸、壬基酚、雙酚A )之成分及其生物毒性。同時檢測各消毒副產物原體之螢光生物毒性，用以比對各自來水廠之各枯水期及豐水期之原水與清水中消毒副產物生物毒性標準。自來水廠水樣採用固相萃取法，以TC-18萃取管柱萃取，利用分離、萃取方式以去除干擾物質，萃取之水樣，利用Microtox及化學分析檢測水樣有機物質成分及生物毒性。
實驗結果顯示，水中消毒副產物毒性在品保標準下，螢光生物法之毒性強弱依序是環境荷爾蒙>鹵乙酸>三鹵甲烷，5分鐘急毒性EC50值最高是三鹵甲烷類的三氯甲烷>5000 mg/l，最低是環境荷爾蒙類的壬基酚2.2 mg/l，結果中證實壬基酚生物毒性最強，三氯甲烷生物毒性最弱。原水加氯消毒後產生的副產物成份含量依序是三鹵甲烷>鹵乙酸>環境荷爾蒙，與毒性成反比，鹵乙酸在消毒副產物中所佔量次多，毒性比三鹵甲烷高8~10倍。所以最需要注意的是鹵乙酸在水中加氯消毒的生成。
2009年台灣四個自來水淨水廠於豐、枯水期之各水廠之原、清水之Microtox檢測結果，顯示各自來水淨水廠依Microtox偵測法均不含毒性，枯水期鳳山之原水及豐原水之EC20值分別為43.09 μl及52.70 μl，僅顯示豐原、鳳山之原水水質較福興、板新之原水質較佳，清水水質均安全穩定。
豐水期之EC50及EC20值，顯示各自來水淨水廠原、清水均未達EC50值，顯示各自來水淨水廠綜合化合物，此濃度範圍內，對人體健康影響潛勢較不明顯，鳳山水廠之原水之EC20值較板新豐原及福興淨水廠比較，顯示鳳山水廠之原水之EC20值較板新、豐原及福興水質較佳，但清水各廠水質均未達EC20顯示各自來水淨水廠，清水水質均佳。

枯水期各廠原、清水毒性普遍高於豐水期各廠，原因可能是因為枯水期降雨量較低導致原水中物質有濃縮現象，豐水期雨量較佳原水反而會比枯水期濃度要來的低。

In this research, Bensin Water Treatment Plant, Fong-yuan Water Treatment Plant, Fusing Water Treatment Plant and Fongshan Water Treatment Plant dry season and flood season concentration of disinfection by products trihalomethanes (THMs), haloacetic acids (HAAs) , nonylphenol (NP) and bisphenol A ( BPA) by chemical analysis and fluorescence bioassay (Microtox) in raw water and hydrophile''s were detected. And research also focus on technical grade of disinfection by products as the standards for the detection fluorescence bioassay toxicity of raw water and purified water in each water treated plant at dry and flood season for further advanced study. Tap water sample were through extraction process by TC-18 extraction column in solid phase extraction method. Achieve separation, extracion and removal of interfering substances at the same time. After extraction , the water sample were tested by Microtox (fluorescence bioassay) method.
The results showed toxicity with the water disinfection by-product under quality control standards, the fluorescence bioassay toxicity order of the strength of the EHs> HAAs> THMs, 5 minutes maximum value of acute toxicity EC50 is like THMs’s chloroform (CHCl3)>5000 mg/l, The lowest EHs of NP 2.2 mg/l, the results confirmed that most of NP toxicity, chloroform toxicity weakest. Raw water chlorination by-products resulting from the content are THMs > HAAs> EHs, and biotoxicity is inversely, proportional to HAAs disinfection by-products in the share volume times more toxic than the high THMs 8 -10 times.
So the most important to note were that HAAs formation of chlorination in the water treatment. The Microtox test results in dry season and flood season at Taiwan''s 4 water purification factory in 2009, show that the water purification factory test by Microtox detection method are non-toxic. The raw water in Fongshan and the water in Fong-yuan''s EC20 values are 43.09 μl and 52.70 μl, and only show Fong-yuan and Fongshan''s raw water quality better than Fusing and Bensin''s. The hydrophile quality both are stability.
EC50 and EC20 of the flood season, show the pruification factory''s raw water and hydrophile were not reached to EC50 values.Indicating the field of integrated water purification compounds, the concentration range of potential human health effects were less obvious, The EC20 of Fongshan Water Treatment Plant''s raw water compare Bensin, Fong-yuan and Fusing''s Water Treatment Plant, shows up the EC20 of Fongshan Water Treatment Plant''s raw water quality better than Bensin、Fong-yuan and Fusing. But the hydrophile are all not up to EC20, shows up all water factories, water''s quality are good.
The water toxicity in dry season is higher than flood season generally, The reason could be the rainfall is low, and caused the substances in raw water has concentrated, instead the raw water of flood season''s rainfall lower than dry season.

目錄
中文摘要 I
英文摘要 III

誌謝 V

目錄 VI

表目錄 X

圖目錄 XII

第一章 前言 1
1.1 研究緣起 1
第二章 文獻回顧 3
2.1 水中毒性物質 3
2.2 消毒副產物（Disinfection by products, DBPs） 4
2.2.1 造成DBPs生成之因素 4
2.2.1.1 前驅物質(Precursors) 5
2.2.1.2 有機物的含量 7
2.2.1.3 季節性變化 7
2.2.1.4 加氯量 7
2.2.1.5 pH值 8
2.2.2 消毒副產物 8
2.2.3 消毒副產物種類 10
2.2.4 消毒副產物對人體健康之影響 11
2.3 三鹵甲烷(Trihalomethanes, THMs) 11
2.4 鹵乙酸(haloacetic acids, HAAs) 17
2.5 環境荷爾蒙((Environmental Hormones, EHs) 22
2.5.1 雙酚A(Bisphenol A, BPA) 24
2.5.2 壬基酚(Nonylphenol, NP) 26
2.6 Microtox螢光菌急毒性試驗 30
2.6.1 Microtox 測試原理 30
2.6.2 Microtox之優點 31
2.6.3Microtox之限制 31
2.6.4Microtox應用範圍 33
2.7 Microtox應用相關研究 33
2.7.1 檢測海洋沿海環境品質 33
2.7.2 檢測藻類毒性 34
2.7.3 檢測廢水處理 34
2.7.4 檢測室外空氣中揮發性有機物 35
2.7.5 發光細菌法在土壤質量監測 35
2.8生物毒性效應分級 36
第三章 材料與方法 37
3.1研究流程規劃 37
3.2 水樣採集分析 38
3.2.1 採樣地點與頻率 39
3.2.2 採樣程序 40
3.3 水樣分析方法 41
3.3.1 pH/ORP 41
3.3.2 溶氧(DO) 41
3.3.3 導電度(EC) 42
3.4 固相萃取濃縮之設備與方法 42
3.4.1 TC18 規格 42
3.4.2 四頻道蠕動幫浦 43
3.5 自來水水樣固相萃取 44
3.5.1 樣品保存 44
3.5.2 固相萃取原理 44
3.5.3 固相萃取法 44
3.5.4 管柱適化（column condition） 45
3.5.5 加入樣品（sample loading） 45
3.5.6 沖堤（elute） 45
3.5.7 固相萃取流程 46
3.6 螢光菌急毒性試驗－Microtox 48
3.6.1 儀器設備Microtox Model 500 48
3.6.2 Microtox試驗材料 48
3.6.3 消毒副產物之標準品化學品 50
3.6.4 試驗方法 50
3.6.4.1 試驗流程 52
3.6.5 Microtox試驗品保 53
3.6.6結果分析 54
第四章 結果與討論 56
4.1 三鹵甲烷 56
4.2 鹵乙酸 61
4.3壬基酚與雙酚A 63
4.4 pH、ORP、DOC、餘氯之檢測 66
4.5生物檢測 68
4.5.1三鹵甲烷類原體毒性調查 68
4.5.2鹵乙酸類標準品毒性調查 69
4.5.3環境荷爾蒙類原體毒性調查 71
4.5.4 phenol與 methanol標準品毒性調查 72
4.5.5台灣2009年板新（北）、豐原（中）、鳳山（南）、福（地下水）等四個淨水廠豐、枯水期毒性之各水廠之原、清水調查 73
4.6給水處理方法與風險評估 77
4.7化學與生物分析相關性 79
第五章 結論與建議 81
5-1結論 81
5-2建議 83
參考文獻 84
附錄A Microtox的準確性與靈敏度
表目錄
表1 影響DBPs生成因子 5
表2 天然有機物與消毒副產物之相關性 9
表3 消毒副產物之分類 10
表4 消毒副產物之三鹵甲烷致突變性 13
表4 消毒副產物之三鹵甲烷致突變性(續) 14
表5 三鹵甲烷對囓齒目動物之致癌性 15
表5 三鹵甲烷對囓齒目動物之致癌性(續) 16
表6 鹵乙酸類之物種、中英文名稱及化學式 17
表7 消毒副產物鹵乙酸之致突變性 21
表8 雙酚A基本物化特性 25
表9 壬基酚基本物化特性 27
表10 細菌性生物毒性試驗的特色 32
表11 調查各水廠枯水期原水與清水之三鹵甲烷化學分析濃度 58
表12 調查自來水廠豐水期原水與清水之三鹵甲烷化學分析濃度 59
表13 各地區對DBPs之相關規範 60
表14 調查廠址枯水期原水與清水之鹵乙酸分析濃度 62
表15 調查廠址豐水期原水與清水之鹵乙酸分析濃度 63
表16 調查廠址枯水期原水與清水之壬基酚及雙酚A濃度 64
表17 調查廠址豐水期原水與清水之壬基酚及雙酚A濃度 65
表18 西班牙原水雙酚A經各淨水單元處理後之濃度變化 65
表19 調查廠址枯水期原水與清水之pH值 66
表20 調查廠址豐水期原水與清水之pH值 67
表21 調查廠址枯水期原水與清水之DOC濃度 67
表22 調查廠址豐水期原水與清水之DOC濃度 67
表23 利用螢光偵測法(Microtox)偵測三鹵甲烷類二氯一溴甲烷與三氯甲烷原體藥物之EC50及EC20值 69
表24 利用螢光偵測法(Microtox)偵測鹵乙酸類氯乙酸、二氯乙酸及三氯乙酸原體藥物之EC50及EC20值 70
表25 利用螢光偵測法(Microtox)偵測鹵乙酸類的溴乙酸與二溴乙酸原體藥物之EC50及EC20值 71
表26 利用螢光偵測法(Microtox)偵測環境荷爾蒙類的壬基酚與雙酚A 原體藥物之EC50及EC20值 72
表27利用螢光偵測法(Microtox)偵測苯酚與甲醇藥物之EC50及EC20值 73
表28 利用螢光偵測法(Microtox)於2009年偵測台灣四個自來水淨水廠枯水期之各水廠原、清水樣本之EC50及EC20值 75
表29 利用螢光偵測法(Microtox)於2009年偵測台灣四個自來水淨水廠豐水期之各水廠原、清水樣本之EC50及EC20值 76
表30大陸與加拿大給淨水廠飲用水之致癌風險潛勢 78
表31台灣北中南地區給淨水廠飲用水之致癌風險潛勢 78
表32台灣各地區給淨水廠飲用水之致癌風險潛勢 79
圖目錄
圖1 三鹵甲烷結構式 12
圖2 US EPA 規範之五種鹵乙酸結構式 18
圖3 雙酚A之化學結構式 25
圖4 環氧樹酯之化學結構式 26
圖5 壬基酚類持久性有機污染物結構 28
圖6 研究流程規劃圖 38
圖7 採樣流程圖 39
圖8 採樣作業程序流程圖 40
圖9 基本分析流程圖 41
圖10 TC-18萃取管柱 43
圖11 四頻道蠕動幫浦 43
圖12 水樣固相萃取流程圖 47
圖13 毒性物質分析儀(Microtox Model 500) 48
圖14 螢光生物毒性(Microtox)檢測設備 49
圖15 Microtox試驗流程圖 53

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