利用同位衍生/萃取結合微波輔助頂空固相微萃取法檢測水樣中的烷基酚類化合物

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吳羽珮(Yu-pei Wu) 查詢紙本館藏

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化學學系

論文名稱

利用同位衍生/萃取結合微波輔助頂空固相微萃取法檢測水樣中的烷基酚類化合物
(One-step in situ derivatization/extraction coupled with microwave- assisted HS-SPME to detect alkylphenols in aqueous samples)

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摘要(中)

烷基酚(alkylphenols)為烷基酚聚乙氧基醇類(alkylphenol polyethoxylates，簡稱APnEOs)非離子型界面活性劑在環境中所降解的產物，已被證實會干擾生物體的內分泌機制，被稱之為環境荷爾蒙(environmental hormones)。此類化學物質近年來引起了大眾的關注，故有必要發展一套既快速又便利的方法檢測環境中的烷基酚類化合物。
　　在本篇研究中，利用一步完成的微波輔助固相微萃取法(Microwave-Assisted Headspace Solid-Phase Microextraction，簡稱MA-HS-SPME)搭配同位衍生(in situ derivatization)的方式來當作樣品的前處理步驟，再結合氣相層析質譜儀(GC-MS)來偵測水樣中的烷基酚類化合物。取20 mL水樣置於40 mL的棕色瓶中，添加1 g的KHCO3 、300 μL的衍生試劑acetic anhydride及2 g的NaCl，使用65 μm PDMS/DVB的纖維於80 W加熱並萃取5分鐘。偵測極限範圍在2及30 ng/L之間，定量極限範圍在5及50 ng/L之間。
　　在環境水樣中，4-t-OP與4-NPs以標準添加法定量的結果分別介於142.9至579.8 ng/L和124.8至933.8 ng/L之間，回歸係數高於0.9669。本研究開發的微波輔助頂空固相微萃取法搭配同位衍生，結合氣相層析質譜儀，是具有快速檢測、步驟簡便及穩定性佳的方法，克服傳統萃取法中耗時且需使用大量有機溶劑的缺點，可用來偵測水樣中的烷基酚類化合物。

摘要(英)

4-tert-octylphenol (4-t-OP) and 4-nonylphenol isomers (4-NPs) are two persistent degradation products from widely used nonionic surfactants alkylphenol polyethoxylates (APEOs). They have been demonstrated to exhibit the ability to mimic natural hormones. The large-scale usage of surfactants and increasing public concern over environmental issues has stimulated our interest to investigate their occurrence and behavior in the environment.
The present study described a rapid and solvent-free procedure for the determination of 4-t-OP and 4-NPs in water samples by one-step in situ acetylated coupled with microwave-assisted headspace solid-phase microextraction (MA-HS-SPME) prior to their determination using gas chromatography-mass spectrometry (GC-MS). The effects of various derivatization and extraction parameters were systematically investigated and optimized. Under optimized conditions, 300 μL of acetic anhydride mixed with 1 g of KHCO3 and 2 g of NaCl in a 20-mL water sample (in a 40-mL sample-bottle) were efficiently extracted by a 65 μm polydimethylsiloxane -divinylbenzene (PDMS-DVB) fiber placed in the headspace when the system was microwave irradiated at 80 W for 5 min. The limits of quantification (LOQs) were 5 and 50 ng/L for 4-t-OP and 4-NPs, respectively. The precision for these analytes, as indicated by relative standard deviations (RSDs), were less than12.9 % for both intra- and inter-day analysis. Accuracy, expressed as the mean extraction recovery, was between 49.9 – 81.8 % and 27.7 – 63.2 % for 4-t-OP and 4-NPs, respectively. A standard addition method was used to quantitate 4-t-OP and 4-NPs, and the concentrations ranged from 142.9 to 579.8 ng/L and 124.8 to 933.8 ng/L for 4-t-OP and 4-NPs, respectively in various environmental samples. This in situ acetylated MA-HS-SPME appears to be a good alternative extraction method for the determination of 4-t-OP and 4-NPs in environmental samples; it is a simple, effective, low-cost, and eco-friendly analytical method.

關鍵字(中)

★ 烷基酚類化合物
★ 微波輔助
★ 同位衍生
★ 頂空固相微萃取法

關鍵字(英)

★ HS-SPME
★ microwave- assisted
★ in situ derivatization
★ alkylphenols

論文目次

目錄
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 4
第二章　文獻回顧 5
2-1　環境荷爾蒙 5
2-1-1　何謂環境荷爾蒙 5
2-1-2　環境荷爾蒙的作用機制 6
2-1-3　烷基酚類化合物 7
2-1-4　烷基酚類化合物毒性 10
2-1-5　環境中烷基酚類化合物的含量 17
2-1-6　人體暴露之風險評估 18
2-1-7　相關研究文獻 21
2-2　微波 23
2-2-1　微波簡介 23
2-2-2　加熱原理 24
2-2-3　微波裝置 26
2-2-4　相關應用 28
2-3　固相微萃取法 30
2-4　衍生化技術 36
2-4-1　乙醯化衍生法 36
2-5　氣相層析質譜儀 38
2-5-1　離子阱質譜儀 41
2-6　標準添加法 42
第三章　實驗步驟與樣品分析 44
3-1　實驗藥品與設備 44
3-1-1　實驗藥品 44
3-1-2　儀器設備 45
3-2　實驗步驟 46
3-2-1　標準品的配製 46
3-2-2　氣相層析質譜儀的參數設定 46
3-2-3　MA-HS-SPME裝置 48
3-2-4　操作流程 48
3-3　水樣採集 50
3-4　真實樣品檢測定量 51
第四章　結果與討論 52
4-1　氣相層析質譜儀對烷基酚類化合物的測定 52
4-1-1　烷基酚類化合物的分析 52
4-1-2　儀器的偵測極限 52
4-2　乙醯化衍生條件的最佳化 57
4-3　微波輔助萃取條件最佳化 59
4-4　固相微萃取法的條件最佳化 62
4-4-1　萃取纖維的種類 62
4-4-2　熱脫附溫度 63
4-4-3　熱脫附時間 65
4-4-4　NaCl添加量 66
4-5　微波輔助頂空固相微萃取法搭配乙醯化衍生的最佳化結果 68
4-6　微波輔助頂空固相微萃取法搭配乙醯化衍生之檢量線 69
4-7　真實水樣定量 71
第五章　結論與建議 78
5-1　結論 78
5-2　建議 78
第六章　參考文獻 79
附錄 86
圖目錄
圖1-1.　雌激素與壬基酚化合物的結構 3
圖2-1.　環境荷爾蒙與天然荷爾蒙的關係圖 7
圖2-2.　烷基酚聚乙氧基醇類非離子型界面活性劑之結構 9
圖2-3.　烷基酚類化合物的結構 10
圖2-4.　烷基酚聚乙氧基醇類於環境中降解的途徑 11
圖2-5.　一般電磁波頻率範圍示意圖 24
圖2-6.　微波加熱原理示意圖 27
圖2-7.　微波加熱與傳統加熱法的比較示意圖 28
圖2-8.　固相微萃取裝置圖 31
圖2-9.　固相微萃取法的操作過程 32
圖2-10.　固相微萃取塗覆固定相的種類與性質 34
圖2-11.　乙醯化衍生反應 37
圖2-12.　氣相層析儀構造圖 39
圖2-13.　質譜儀構造圖 39
圖2-14.　離子阱結構圖 41
圖2-15.　標準添加法操作圖 43
圖2-16.　標準添加法檢量線 43
圖3-1.　MA-HS-SPME裝置圖 48
圖4-1.　烷基酚類化合物的質譜圖 53
圖4-2.　衍生前後的汲取質量層析圖 54
圖4-3.　衍生前後的效果比較 55
圖4-4.　烷基酚類化合物的汲取質量層析圖 56
圖4-5.　乙醯化衍生條件對萃取量的影響 58
圖4-6.　加熱瓦數與萃取時間對萃取量的影響 61
圖4-7.　萃取纖維對萃取量的影響 63
圖4-8.　脫附溫度對脫附量的影響 64
圖4-9.　脫附時間對脫附量的影響 66
圖4-10.　NaCl添加量對萃取量的影響 67
圖4-11.　微波輔助頂空固相微萃取法搭配乙醯化衍生之檢量線 70
圖4-12.　竹科放流口的汲取質量層析圖 72
圖4-13.　老街溪的汲取質量層析圖 73
圖4-14.　百花川上游的汲取質量層析圖 73
圖4-15.　百花川中游的汲取質量層析圖 74
圖4-16.　百花川下游的汲取質量層析圖 74

表目錄
表2-1.　烷基酚類化合物的相關性質 9
表2-2.　烷基酚類化合物在水生生物的BCF值(WET WEIGHT) 14
表2-3.　壬基酚的急毒性表 15
表2-4.　辛基酚的急毒性與慢毒性表 16
表2-5.　各國廢汙水廠放流水之烷基酚濃度 17
表2-6.　各國河水之烷基酚濃度 18
表2-7.　液態樣品的萃取方法 22
表3-1.　整合離子層析模式下定量離子 47
表4-1.　烷基酚類化合物之儀器偵測極限與線性關係 56
表4-2.　KHCO3與ACETIC ANHYDRIDE之衍生條件 58
表4-3.　加熱瓦數與時間之萃取條件 60
表4-4.　烷基酚類化合物的偵測極限與線性關係 70
表4-5.　環境樣品的電導度值 72
表4-6.　標準添加法所得的線性關係 75
表4-7.　方法的穩定性與再現性 76
表4-8.　本實驗方法與其他文獻的比較 77

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指導教授

丁望賢(Wang-hsien Ding)

審核日期

2011-6-23

推文