以振盪輔助分散式液液微萃取法檢測環境水樣中含氮消毒副產物

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研究生：	郭逸民 Yi-min Kuo
論文名稱：	以振盪輔助分散式液液微萃取法檢測環境水樣中含氮消毒副產物
指導教授：	丁望賢 Wang-Hsien Ding
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 化學學系 Department of Chemistry
論文出版年：	2014
畢業學年度：	102
語文別：	中文
論文頁數：	132
中文關鍵詞：	氣相層析質譜儀、含氮消毒副產物、鹵化乙腈
外文關鍵詞：	GC/MS, Haloacetonitrile, N-DBPs
相關次數：	點閱：8 下載：0
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含氮消毒副產物(Nitrogenous disinfection by-products, N-DBPs)近年來被發現在我們一般所使用的自來水中，來源是由於我們對水進行消毒時，一些天然的含氮有機物被氯化所產生，而對於一般的消毒副產物來說，含氮消毒副產物在動物的研究中被認為有更高的致癌性及致畸性，並且有可能會經由飲食或是其他途徑來危害到人類的健康，近年來已被歸類為新興汙染物(Emerging contaminants，ECs)的一種。

本研究是利用振盪輔助分散式液液微萃取法(vortex-assisted dispersive liquid-liquid microextraction, VADLLME)搭配氣相層析質譜儀檢測水體中的含氮消毒副產物-鹵代乙腈(Haloacetonitrile, HANs)，並利用實驗統計設計及變異數分析做最佳化的探討。最佳化後的萃取條件為:以8.0 mL水樣調pH值為4時，加入2.64 g氯化鈉，待完全溶解後，以160 μL的二氯甲烷(dichloromethane, DCM)做為萃取劑，並使用超快速振盪機(VOTEX)均勻混合1分鐘，最後再以離心機6000 rpm離心3分鐘後，將下沉液取出。取9 μL待測物溶液並加入1 μL內標準品後，利用大體積樣品導入裝置導入GC注射埠中，搭配氣相層析質譜儀(gas chromatography- mass spectrometry, GC-MS)來偵測，可得偵測極限皆小於0.2 μg/L。並且在檢測水樣中，四個鹵代乙腈成份的總濃度介於1.1至9.7 μg/L。

Haloacetonitriles (HANs) are a class of nitrogen-containing disinfection by-products (N-DBPs) that have been found in our drinking water, because of using disinfectants in drinking water treatment leads to the formation from the chlorination of natural organic matter (NOM). Some reports indicate that N-DBPs are more toxic and carcinogenic than the regulated DBPs, and N-DBPs have been associated with a number of adverse human health effects. N-DBPs are considered as one of the emerging pollutants in the environment.
In this study, a simple, robust, and fast procedure, Vortex-assisted dispersive liquid-liquid microextraction (VADLLME) with GC-MS for the determination of HANs: trichloroacetonitrile (TCAN), dichloroacetonitrile (DCAN), bromochloroacetonitrile (BCAN) and dibromoacetonitrile (DBAN) in drinking water samples. The parameters affecting the VADLLME efficiency were systematically investigated by statistical experimental design and analysis of variance. For optimal conditions of VADLLME are：the rapid injection of 160 μL of dichloromethane (as an extractant) into 8 mL of water containing 33% of sodium chloride and pH 4 in a conical bottom glass tube. After vortex for 1 min and centrifugation for 3 min at 6,000 rpm(ca. 3940 g). The extract 9 L and 1 L internal standard were then directly determined by large-volume injection gas chromatography with mass spectrometry (GC-MS) .
The limits of quantitation (LOQs) were less than 0.2 μg/L. Total concentrations of four HANs in water samples were detected ranging 1.1-9.7 μg/L.

摘要        I
Abstract       II
謝誌     IV
目錄      V
圖目錄        IX
表目錄       XII
第一章 前言      1
1-1 研究緣起   1
1-2 研究目標   3
第二章 文獻回顧    5
2-1 消毒副產物      5
2-1-1 消毒副產物簡介 (Disinfection by-products, DBPs)       5
2-1-2 含氮消毒副產物 (Nitrogenous disinfection by-products,
N-DBPs)   7
2-1-3 鹵代乙腈的形成機制   8
2-1-4 鹵代乙腈的性質         10
2-2 氣相層析質譜儀       15
2-2-1 大體積直接進樣裝置       17
2-2-2 離子阱質譜儀       19
2-3 分散式液液微萃取法       21
2-3-1 前言    21
2-3-2 分散式液液微萃取法原理      23
2-3-3 分散式液液微萃取法流程      23
2-3-4 影響分散式液液微萃取法之因素      25
2-3-5 分散式液液微萃取法的發展        28
2-3-6 振盪輔助分散式液液微萃取法(Vortex-assisted dispersive
liquid-liquid microextraction，簡稱VADLLME)      33
2-4 實驗設計        35
2-4-1 實驗設計簡介       35
2-4-2 反應曲面法(Response surface methodology, RSM)     37
2-4-3 Box-Behnken 設計    41
2-5 線性迴歸        43
2-6 基質效應        47
第三章 實驗步驟與樣品分析      51
3-1 實驗藥品與設備       51
3-1-1 實驗藥品        51
3-1-2 儀器設備        53
3-2 實驗步驟        54
3-2-1 標準品的配置       54
3-2-2 氣相層析質譜儀的參數設定        55
3-2-3 實驗流程        57
3-3 水樣採集        58
第四章 結果與討論     59
4-1 氣相層析質譜儀對鹵代乙腈待測物的測定        59
4-1-1 鹵代乙腈待測物的分析   59
4-1-2 鹵代乙腈待測物質譜圖   61
4-1-3 檢量線及偵測極限     65
4-2 振盪輔助分散式液液微萃取法最佳化條件探討      66
4-2-1 萃取劑種類選擇         66
4-2-2 鹽類的添加量       68
4-2-3 水樣的體積    70
4-2-4 萃取時間        71
4-2-5 統計實驗設計做VADLLME 最佳化        73
4-2-6 因子間交互作用力的探討      79
4-3 Mandel test 與 Matrix effect     83
4-3-1 Mandel test   83
4-3-2 The Lack-of-fit test    84
4-3-3 Matrix effect        85
4-4 真實樣品之檢測     87
4-4-1 自來水樣品的檢測   87
4-4-2 游泳池水樣品的檢測     95
4-5 檢測方法的穩定性      101
第五章 結論        103
第六章 參考文獻       105
                                

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