以矽烷化衍生試劑搭配氣相層析質譜儀於線上衍生法快速分析環境水樣中三氯沙之濃度

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鄭喬尹(Chiao-yin Cheng) 查詢紙本館藏

畢業系所

化學學系

論文名稱

以矽烷化衍生試劑搭配氣相層析質譜儀於線上衍生法快速分析環境水樣中三氯沙之濃度
(Determination of Triclosan in Water Samples by On-line Derivatizaion coupled with Gas Chromatography-Mass Spectrometry)

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摘要(中)

本篇研究主要是以氣相層析質譜儀的大體積進樣裝置搭配矽烷化衍生試劑進行注射埠之線上衍生化技術，有效檢測環境水樣中的三氯沙(TCS)與甲基三氯沙(MTCS)。在衍生化的過程中，針對注射埠中的反應溫度及時間進行最佳化探討，以MTBSTFA作為衍生試劑，衍生反應溫度及時間分別為120℃和2分鐘，可將TCS轉化成TCS-TBDMS衍生物，在進行GC檢測時，能與MTCS完全分離。線上衍生技術步驟簡單且能迅速地分析待測物，簡化傳統衍生反應的過程與衍生試劑用量，並利用固相萃取技術作為水樣的前處理方法。待測物在去離子水中之回收率為104%以上，相對標偏差值(RSD)則都在7%以下。對台灣不同環境樣品進行檢測，待測物的回收率大多可在70%以上，相對標準偏差在12%以下，而本方法之定量偵測極限(LOD)對三氯沙及甲基三氯沙分別為0.9 ng/L與1.0 ng/L。針對安平污水處理廠之進流水中，檢測出三氯沙的濃度範圍為35 ng/L至278 ng/L，放流水則為78 ng/L以下；豐原地區表面水水樣品與中央大學百花川水樣中觀察到微量的三氯沙存在，濃度範圍約1~70 ng/L之間。在所有環境水樣中均未檢測到甲基三氯沙。除此之外，本篇研究也針對市售的個人護理產品(如洗面乳、牙膏和洗手乳)以超音波震盪的萃取方式進行檢測，三氯沙的濃度範圍為0.07% ~ 0.28%，均在政府的規範內。

摘要(英)

A rapid injector-port derivatization with gas chromatography-mass spectrometry (GC-MS) method was developed and validated for the determination of triclosan (TCS) and methyl triclosan (MTCS) in various environmental water samples. The parameters related to the derivatization process (i.e., injection-port temperature and reaction time) were optimized. TCS was converted into the tert-butydimethylsilyl (TBDMS) derivative by MTBSTFA as silyation reagent holding 2 min in injection-port at temperature 120℃. Derivative TCS-TBDMS can be separated from MTCS in GC analysis. This technique simplified the derivatization procedure and increase sensitivity.
Solid-phase extraction (SPE) method was used to cleanup and concentrate analytes from wastewater samples. The limits of detection of TCS and MTCS were 0.9 and 1.0 ng/L, respectively. The recoveries from the spiked water samples ranged from 48 – 119% with relative standard deviation (RSD) less than 16% at the 250 ng/L level. Only TCS was detected in wastewater and surface water samples, and concentrations ranged from 35 - 287 ng/L in influents, ND - 78 ng/L in effluents, 1 - 70 ng/L in surface water samples. No MTCS was detected in all samples.
In this study, we also detected the personal care products (i.e., toothpaste, facial Cleansing cream and handwashs) using ultrasonic extraction to confirm the content of triclosan. The recoveries of triclosan from the spiked PCP samples ranged from 94 – 100% with relative standard deviation (RSD) less than 12%, and the contents of triclosan ranged from 0.07% - 0.28%.

關鍵字(中)

★ 線上衍生化
★ 氣相層析質譜儀

關鍵字(英)

★ derivatization
★ gas chromatography-mass spectrometry

論文目次

中文摘要 I
英文摘要 II
謝誌 IV
目錄 V
圖目錄 IX
表目錄 XI
第一章　前言 1
1-1　研究緣起 1
1-2　研究目標 6
第二章　文獻回顧 7
2-1　新興污染物 7
2-1-1　新興污染物的分類和來源 7
2-1-2　新興污染物的隱憂 9
2-1-3　抗菌劑－三氯沙 10
2-1-4　三氯沙的毒性及其對環境之影響 13
2-1-5　相關研究文獻 19
2-2　氣相層析質譜儀 29
2-2-1　氣相層析儀之大體積進樣裝置系統 29
2-2-2　氣樣層析/離子阱質譜儀之原理與特性 32
2-2-3　電子撞擊游離法 36
2-3　衍生化技術 39
2-3-1　衍生化技術的種類和條件 39
2-3-2　矽烷化衍生法 41
2-3-3　線上衍生技術 43
2-4　固相萃取法 46
第三章　實驗步驟與樣品分析 50
3-1　實驗藥品與設備 50
3-1-1　實驗藥品 50
3-1-2　儀器設備 52
3-2　實驗步驟 53
3-2-1　標準品的配製 53
3-2-2　氣相層析質譜儀的參數設定 55
3-2-3　線上衍生化步驟 56
3-2-5　固相萃取步驟 57
3-2-6　個人產品萃取步驟 58
3-3　水樣採集 58
第四章　結果與討論 60
4-1　衍生化試劑之探討 60
4-1-1　衍生試劑的選擇 60
4-1-2　對掌異構物之分離 63
4-2　不同反應條件對衍生化效率之探討 64
4-2-1　注射埠溫度對衍生化效率之影響 64
4-2-2　反應時間對衍生化反應之影響 65
4-2-3　衍生化試劑體積之影響 66
4-2-4　分析物的測定 67
4-3　檢量線 71
4-4　市售個人護理產品之成分確認 74
4-5　固相萃取 79
4-5-1　沖提溶劑的選擇 79
4-5-2　方法的穩定度與再現性 82
4-6　真實水樣之分析結果 83
第五章　結論與建議 95
5-1　結論 95
5-2　建議 96
第六章　參考文獻 97
附錄 105
A-1　衍生化試劑效果之實驗數據 105
A-2　衍生化溫度對衍生化效果之實驗數據 105
A-3　衍生化時間對衍生化效果之實驗數據 106
A-4　衍生化試劑劑量對衍生化效果之實驗數據 106

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指導教授

丁望賢(Wang-Hsien Ding)

審核日期

2009-6-28

推文