以分散微固相萃取法搭配氣相層析質譜儀快速檢測水樣中之NDMA

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研究生：	傅思潔 Ssu-chieh Fu
論文名稱：	以分散微固相萃取法搭配氣相層析質譜儀快速檢測水樣中之NDMA Determination of NDMA in Aqueous samples by using dispersive Micro Solid Phase Extraction coupled with gas chromatography/mass spectrometry
指導教授：	傅思潔 Ssu-chieh Fu 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
畢業學年度：	99
語文別：	中文
論文頁數：	119
中文關鍵詞：	NDMA 、微固相萃取法
外文關鍵詞：	micro-solid phase extraction, NDMA
相關次數：	點閱：12 下載：0
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使用消毒劑消毒水源是為了消滅水中致病菌，但使用消毒劑卻會無預期地產生對人體健康有害的副產物，而其中一種具毒性的消毒副產物，二甲胺亞硝基(N-nitrosodimethylamine，簡稱NDMA)增加了致癌風險，因此水中的NDMA是目前大眾關心的新興議題，NDMA已被US-EPA歸類為非常規性的汙染物(UCMR-2)，但尚未制定明確的限制含量。
在本篇研究中，發展一套簡便的樣品前處理方法，分散微固相萃取法(Dispersive Micro Solid Phase Extraction，簡稱dMSPE)，利用此方法萃取水樣因氯消毒而產生的NDMA，以及不同碳鏈的亞硝胺類化合物，再結合氣相層析質譜儀做為檢測工具。
本研究探討了影響dMSPE萃取效率的參數並將其最佳化。最佳化實驗萃取條件是使用商業化的碳分子篩－Carboxen 1003，加入其75 mg於含氯化鈉至5% 的50 mL水樣中，搖盪20分鐘完成萃取後，快速過濾吸附劑後以150 μL的二氯甲烷回溶。萃取完成後直接取10 μL以直接進樣裝置導入氣相層析質儀，以化學游離法和選擇離子儲存模式進行分析，可測得亞硝胺的定量極限小於0.9 ng/L。在真實水樣的應用中，可測得室內/外游泳池水中含有NDMA，濃度介於4.7－127.4 ng/L間，萃取回收率在57－114%間，相對標準偏差小於20%。本研究發展的dMSPE是個簡便並且使用微量有機溶劑的前處理技術，即可有效的萃取水樣中的NDM即其它亞硝胺類。

Abstract
Disinfection has successfully applied to eliminate pathogens in various water supplies, however its byproducts (DBPs) cause unintended health risks to human. N-nitrosodimethylamine (NDMA) is one of the most toxic DBPs that raises the cancer risk. Due to its high toxicity, nowadays, the presence of NDMA and other N-nitrosamines in water is an emerging issue since many of them are suspected to be human carcinogens. They are also listed in the Unregulated Contaminant Monitoring Rule 2 (UCMR-2) by US-EPA.
In this study, a simple sample pretreatment technique, dispersive micro-solid phase extraction (dMSPE), was developed for the extraction of NDMA and other N-nitrosamines (NAs) from aqueous samples. The parameters affecting the extraction efficiency were systematically investigated and the conditions optimized. The best extraction conditions involved the immersed 75 mg of carbon molecular sieve, carboxen 1003 (as adsorbent), in a 50 mL water sample containing 5% of sodium chloride in a sample tube. After 20 min of shaking extraction, the adsorbent was collected under rapidly filtered, and 150 ?L of dichloromethane was used to elute NAs from the adsorbent. The extract 10 ?L was then directly determined by large-volume injection gas chromatography with chemical ionization mass spectrometry (GC-CI/MS) under selected ion storage mode. The limits of quantitation (LOQs) were less than 0.9 ng/L. The method was validated through a recovery study of various environmental
III
samples. Concentrations of NDMA in swimming pool water samples were detected ranging 4.7 to 127.4 ng/L, and recovery ranged from 57-113% and the relative standard deviation was below 20%. This developed method is a simple and solvent-less pretreatment method to detect NDMA and other N-nitrosamines in aqueous sample.

目錄
中文摘要 ............................................................................................................... I
英文摘要 .............................................................................................................. II
謝誌 .................................................................................................................... IV
目錄 ..................................................................................................................... V
圖目錄 ............................................................................................................. VIII
表目錄 ................................................................................................................. X
第一章 前言 ...................................................................................................... 1
1-1 研究緣起 ............................................................................................. 1
1-2 研究目標 ............................................................................................. 4
第二章 文獻回顧 .............................................................................................. 5
2-1 消毒副產物......................................................................................... 5
2-1-1 NDMA的污染 ........................................................................ 7
2-1-2 NDMA形成機制 .................................................................... 8
2-1-3 亞硝胺性質 ........................................................................... 14
2-1-4 亞硝胺毒性 ........................................................................... 18
2-1-5 相關研究文獻 ....................................................................... 23
2-2 氣相層析質譜儀 .............................................................................. 30
2-2-1 大體積直接進樣裝置 ........................................................... 32
VI
2-2-2 離子阱質譜儀 ....................................................................... 34
2-2-3 化學游離法 ........................................................................... 35
2-2-4 選擇離子掃瞄模式 ............................................................... 38
2-3 分散微固相萃取法 .......................................................................... 40
2-3-1 分散固相萃取法歷史沿革 ................................................... 40
2-3-2 吸附原理 ............................................................................... 42
2-3-3 分散微固相萃取法原理 ....................................................... 46
2-3-4 影響分散微固相萃取的因素 ............................................... 48
2-3-5 相關應用 ............................................................................... 51
第三章 實驗步驟與樣品分析 ........................................................................ 52
3-1 實驗藥品與設備 .............................................................................. 52
3-1-1 實驗藥品 ............................................................................... 52
3-1-2 儀器設備 ............................................................................... 54
3-2 實驗步驟 ........................................................................................... 55
3-2-1 標準品的配製 ....................................................................... 55
3-2-2 氣相層析質譜儀的參數設定 ............................................... 56
3-2-3 分散微固相萃取步驟 ........................................................... 59
3-3 真實樣品測樣採集 .......................................................................... 60
第四章 結果與討論 ........................................................................................ 61
VII
4-1 亞硝胺化合物的分析 ...................................................................... 61
4-1-1 化學游離法 ........................................................................... 61
4-1-2 儀器的偵測極限 ................................................................... 67
4-2 分散微固相萃取法模擬水樣最佳化條件最佳化探討 .................. 69
4-2-1 吸附劑種類選擇 ................................................................... 69
4-2-2 吸附劑和萃取劑 ................................................................... 72
4-2-3 萃取時間 ............................................................................... 78
4-2-4 NaCl添加量 .......................................................................... 80
4-2-5 吸附劑量 ............................................................................... 82
4-3 真實水樣定量 .................................................................................. 85
第五章 結論與建議 ........................................................................................ 95
5-1 結論 ................................................................................................... 95
5-2 建議 ................................................................................................... 95
第六章 參考文獻 ............................................................................................ 96
附錄 ..................................................................................................................101

                                

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