近年來，綠色化學的趨勢逐漸成為全球所關注，如何應用少量的化學藥品達到研究成果，更是被受關注。本文採用動態三液相微萃取（Dynamic-LLLME）強調快速、簡便、低成本及低污染，作為環境水樣中七種苯胺類(aniline；benzidine；o-Toluidine；4-nitroaniline；4-chloroaniline；4-bromoaniline；3,4-dichloroaniline)污染物的濃縮萃取，並使用配合高效液相層析儀/二極體陣列偵測器(HPLC/PDA)進行分離與分析。

本研究的苯胺類化合物已被研究證實有致癌的危險性，其中聯苯胺(Benzidine)被美國國家環境保護署(EPA)列為第一控管污染物。為達低偵測極限，在前濃縮方面探討使用多元醇當萃取液，和添加不同種類的酸研究其對分析物萃取效果之影響，而其他各項可能影響萃取效率的變因也進行詳細探討。並實際應用本方法於環境水樣（寶山水庫水、濁水溪、淡水河）。

於最佳實驗條件下，方法偵測極限（MDLs）在0.1~2.0 μg/L；線性相關係數（r2）在線性濃度範圍內均大於0.9989；線性濃度因不同化合物而異，大致落在0.5~500 μg/L內；精密度方面，相對標準偏差RSD (%)，在試劑水落在3.3~8.4%之間，而在環境水樣落在3.6~9.2%之間。對於準確度的測試，作三種環境水樣的相對添加回收率分別為93.6 %~102.5 %、86.5 %~105.2 %及85.5 %~104.8 %，顯示本分析方法不易受到基質的干擾，可成功應用於環境水樣之分析芳香胺類化合物。

In recent years, green chemistry has become the main point in global chemistry research. In this research ,we use dynamic-LLLME which stress fast、 simple、low-cost and low-pollution technique to concentrate seven aromatic amines(aniline；benzidine；o-Toluidine；4-nitroaniline；4-chloroaniline；4-bromoaniline；3,4-dichloroaniline) in environmental water then separate and determine by high performance liquid chromatography（HPLC）and Photo Diode Array (PDA) detector.
Aromatic amines are proven to be carcinogenic , especially benzidine has been regulated as priority pollutant by U.S. Environmental Protection Agency (EPA) . In order to reach low detection limits, we use polyhydric alcohols as extraction solvent and find that different anion from acid affect extraction . This work also makes a detailed research about other factors that mainly influence extraction results, and applies the proposed method to reservoir water 、stream water and river water.
Under the optimum experiment conditions, method of detection limits（MDLs） range from 0.1~2.0 μg/L; Good linearity of analytes is achieved in the range of 0.5~500 μg/L with coefficients of determination, r2 > 0.9989; Good reproducibilities of extraction performance are obtained with RSD (%)3.3~8.4 in test water and 3.6~9.2 in environmental water .The spiked relative recoveries of the three real samples are in the range of 93.6 %~102.5 %、86.5 %~105.2 % and 85.5 %~104.8 %, respectively. This reveals the proposed method can successfully apply to the analysis of aromatic amine from environmental water samples.

目錄
摘要 II
Abstract IV
目錄 V
表目錄 VIII
圖目錄 IX
第一章 緒論 1
1-1 研究緣起 1
1-2 分析物—芳香胺類化合物 1
1-2-1 芳香胺的特性 2
1-2-2芳香胺族致癌原因 2
1-3 傳統有機污染物的前處理方法 3
1-4目前有機污染物的前處理方法 4
1-5 液相微萃取法 7
第二章 文獻回顧與研究方法 11
2-1 相關前處理技術的文獻回顧 11
2-2 研究方法介紹 12
2-2-1 LLLME原理 12
2-2-2 平衡LLLME [42] 13
2-2-3 非平衡LLLME 14
2-2-4 改變受相極性及搭配不同的酸的影響 14
第三章 實驗部份 16
3-1 試藥 16
3-1-1分析物標準品 16
3-1-2試劑與藥品 16
3-2 標準溶液和真實樣品溶液 17
3-2-1標準溶液 17
3-2-2真實樣品溶液 18
3-3儀器裝置 18
3-4萃取步驟 19
第四章 結果與討論 21
4-1不同酸濃度的水溶液受層 21
4-2乙二醇受層中酸之種類影響 21
4-3乙二醇受層中氫碘酸濃度的改變 22
4-4改變受層有機相種類之影響 22
4-5有機相的選擇 22
4-6受層體積效應 23
4-7攪拌速率的影響 24
4-8萃取時間的影響 24
4-9 添加鹽類的影響 24
4-10分析方法的表現 25
4-11 分析方法於環境樣品的測試 26
第五章 結論 27
第六章 參考文獻 28

表目錄
表1、中空纖維液相微萃取的應用與研究 31
表2、HPLC梯度沖提設定 32
表3、各分析物特定吸收波長 32
表4、最佳化萃取條件 33
表5、分析方法的表現 34
表6、於環境樣品中添加分析物標準品的相對回收率 35
表7、各分析方法比較 35

圖目錄
圖一、台灣河川汙染分佈情形 36
圖二、本文七種分析物的結構 37
圖三、苯胺五種共振 38
圖四、苯胺和烷基胺質子化反應比較 38
圖五、不同取代基苯胺類的酸度係數 39
圖六、單滴微萃取 40
圖七、固相微萃取纖維與固定器 41
圖八、固相微萃取裝置 42
圖九、液相微萃取法之兩相及三相系統 43
圖十、單滴微萃取(drop-in-drop system) 44
圖十一、單滴微萃取 45
圖十二、注射針管壁形成薄膜層 46
圖十三、單滴微萃取(Back extraction) 47
圖十四、液相微萃取的原理 47
圖十五、利用中空纖維取代單滴微萃取的液相微萃取法 48
圖十六、微孔膜液液萃取 48
圖十七、兩步驟中空纖維液相微萃第一步驟 49
圖十八、兩步驟中空纖維液相微萃第二步驟 49
圖十九、水溶液受層中酸濃度的改變 50
圖二十、乙二醇受層中酸之種類影響 50
圖二十一、乙二醇受層中氫碘酸濃度的改變 51
圖二十二、改變受層有機相種類之影響 51
圖二十三、有機相選擇結果 52
圖二十四、受層體積 52
圖二十五、攪拌速率的影響 53
圖二十六、萃取時間的影響 53
圖二十七、添加鹽類的影響 54
圖二十八(A)、萃取未添加分析物的空白水庫水樣的層析圖 55
圖二十八(B) 、萃取添加各分析物定量極限濃度(LOQ)的水庫水樣的 層析圖 55
圖二十九、萃取添加各分析物定量極限濃度(LOQ)的淡水河水樣的層 析圖 56
圖三十、萃取添加各分析物定量極限濃度(LOQ)的濁水溪水樣的層析圖 56

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