博碩士論文 88223012 詳細資訊




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姓名 吳建誼( Chien-Yi Wu)  查詢紙本館藏   畢業系所 化學學系
論文名稱 以固相萃取及氣相層析質譜儀對水環境中壬基苯酚類 持久性有機污染物之分析與研究
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摘要(英) Nonylphenol polyethoxylates (NPEOs) is one of the major classes of nonionic surfactants used in Taiwan and over 48 · 106 kg were produced and consumed each year. However, large quantities of these surfactants in wastewaters are discharged into the rivers directly because of Taiwan’s deficient municipal and industrial wastewater treatments. NPEOs can be biodegraded into: (a) shortening of the polyethoxy chain, resulting in the formation of nonylphenol (NP) and shorter ethoxy chain NPEO residues (such as NP1EO and NP2EO); and (b) carboxylation of the terminal ethoxy or nonyl unit, resulting in the formation of nonylphenol polyethoxy carboxylates (NPECs), or carboxy-nonylphenol polyethoxy carboxylates (CNPECs). We called these compounds as persistent nonylphenolic pollutants. The survey of occurrence and concentration of persistent nonylphenolic compounds in the rivers in Taiwan was undertaken to establish environmental concentrations and to support surface water protection programs.
The method involves extraction of the samples by graphitized carbon black (GCB) solid-phase cartridge, which can be used to extract NP and the degradation products (NPnEC and CNPnEC) simultaneously. These persistent nonylphenolic pollutants were then identified and quantified by large-volume injection GC-MS analysis. This technique provides high precision and sensitivity for persistent nonylphenolic pollutants, to quantitation at < 0.1 ?g/L in 200 ml of water samples. Recovery of nonylphenol (NP) and nonylphenoxyacetic acid (NP1EC) in spiked water samples were 84% (RSD=6.0%, n=5) and 95% (RSD=3.9%, n=5), respectively. Concentrations of nonylphenol (NP) in 19 main rivers of Taiwan were in the range n.d. to 5.1 ?g/L, which are below the threshold concentration (10 ?g/L) for vitellogenin induction in fish. However, 99% of these water samples from rivers exceed the predicted-no-effect concentration (PNEC) 0.33 ?g/L as proposed recently by European Union. The average recovery of the 4-t-OP surrogate for NP analysis was 86% (RSD =10.1%, n=136). The total concentrations of shortened NPEO (i.e., NP1EO and NP2EO) and carboxylates metabolites (i.e., NP1EC, NP2EC, CNP1EC and CNP2EC) in rivers were ranged from n.d. to 115.0 ?g/L. The average recovery of the 4-t-OP1EC surrogate for carboxylated nonylphenolic pollutant analysis was 89% (RSD =11.8%, n=136). The results indicated that the method performed satisfactorily despite the variable compositions of environmental samples.
The significant higher concentrations of carboxylated nonylphenolic pollutants were detected in the river waters as compared to that of NP, NP1EO and NP2EO metabolites. These carboxylated nonylphenolic compounds can be regarded as potential precursors for the formation of nonylphenol under various biotransformation conditions.
關鍵字(中) ★ 壬基苯酚
★ 壬基苯酚類持久性有機污染物
★ 固相萃取
★ 氣相層析質譜儀
關鍵字(英) ★ Nonylphenol
★ Persistent Nonylphenolic Compounds
論文目次 目錄
中文摘要---------------------------------------------------- Ⅰ
英文摘要---------------------------------------------------- Ⅱ
目錄-------------------------------------------------------- Ⅳ
表目錄------------------------------------------------------ Ⅶ
圖目錄------------------------------------------------------ Ⅷ
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-------------------------------------------- 6
2-1 環境荷爾蒙-------------------------------------------- 6
2-1-1 何謂環境荷爾蒙---------------------------------- 6
2-1-2 環境荷爾蒙之種類-------------------------------- 7
2-1-3 環境荷爾蒙之作用機制---------------------------- 8
2-1-4 環境荷爾蒙物質對水生動物之影響------------------ 9
2-2 壬基苯酚聚乙氧基醇類非離子界面活性劑------------------ 11
2-2-1 水環境中壬基苯酚聚乙氧基醇類非離子型界面活性劑
的來源------------------------------------------ 11
2-2-2 壬基苯酚聚乙氧基醇類非離子型界面活性劑的生化
降解-------------------------------------------- 12
2-2-3 壬基苯酚類化合物影響之相關研究------------------ 14
2-3 固相萃取法-------------------------------------------- 16
2-4 氣相層析質譜儀---------------------------------------- 18
2-4-1 大體積直接進樣裝置------------------------------ 19
2-4-2 質譜儀------------------------------------------ 21
2-5 高效液相層析儀---------------------------------------- 23
第三章 實驗步驟與樣品分析----------------------------------- 25
3-1 實驗藥品與儀器設備------------------------------------ 25
3-1-1 實驗藥品---------------------------------------- 25
3-1-2 儀器設備---------------------------------------- 26
3-2 實驗步驟---------------------------------------------- 27
3-2-1 標準品的製備------------------------------------ 27
3-2-2 標準品的測定------------------------------------ 28
3-2-3 萃取步驟---------------------------------------- 31
3-2-4 衍生化步驟-------------------------------------- 32
3-2-5 真實水樣萃取及淨化------------------------------ 33
3-2-6 壬基苯酚羧酸類代謝物(CNPnEC)之收集及測定-------- 33
3-3 樣品採集---------------------------------------------- 34
第四章 結果與討論------------------------------------------- 37
4-1 短鏈式壬基苯酚聚乙氧基醇類的測定---------------------- 37
4-2 短鏈式壬基苯酚聚乙氧基羧酸類的測定-------------------- 40
4-3 壬基苯酚羧酸類化合物(NPnEC)的在烷基鏈上的ω-氧化、β-氧化
降解產物測定------------------------------------------ 42
4-3-1 C7-CNP1EC與C7-CNP2EC之探討---------------------- 48
4-3-2 C9NPnEC之測定----------------------------------- 53
4-4 檢量線------------------------------------------------ 57
4-4-1 NP部分------------------------------------------ 57
4-4-2 NP1EC部分--------------------------------------- 57
4-5 測試不同NP與NP1EC於不同水環境中的萃取回收率----------- 58
4-6 台灣河川環境中壬基苯酚聚乙氧醇類代謝物的含量---------- 59
第五章 結論與建議------------------------------------------- 66
5-1 結論-------------------------------------------------- 66
5-2 建議-------------------------------------------------- 66
參考文獻---------------------------------------------------- 67
附錄-------------------------------------------------------- 75
表目錄
表1-1 壬基苯酚及壬基苯酚類持久性有機污染物與天然雌二醇
荷爾蒙(17β-Estradiol)之相對荷爾蒙效應---------------- 4
表3-1 DSI法注射埠溫度變化及分流-不分流之配合---------------- 30
表3-2 高效液層析儀逆相管柱層析條件-------------------------- 34
表4-1 不同樣品基質中NP與NP1EC的回收率----------------------- 59
表4-2 各河系中NP、NP1EO及NP2EO的含量------------------------ 60
表4-3 各河系中NPnEC及CNPNEC的含量--------------------------- 62
表4-4 各國河川中壬基苯酚及壬基苯酚類持久性有機污染物之濃度
比較-------------------------------------------------- 65
圖目錄
圖1-1 壬基苯酚類持久性有機污染物結構------------------------ 1
圖1-2 壬基苯酚(NP)及雌二醇(Estradiol)化合物的結構----------- 2
圖2-1 壬基苯酚聚乙氧基醇類非離子型界面活性劑---------------- 12
圖2-2 壬基苯酚聚乙氧基醇類遭水環境中微生物分解之降解途徑---- 13
圖2-3 微生物的ω-氧化或β-氧化降解降解途徑------------------ 13
圖2-4 壬基苯酚羧酸類化合物化合物代謝物CNPnEC之結構---------- 15
圖2-5 黑石墨碳(GCB)的結構----------------------------------- 17
圖2-6 固相萃取裝置------------------------------------------ 18
圖2-7 大體積進樣裝置---------------------------------------- 20
圖2-8 質譜儀構造簡圖---------------------------------------- 22
圖2-9 離子阱質譜儀裝置簡圖---------------------------------- 23
圖3-1 台灣部分河川流域圖------------------------------------ 36
圖4-1 NP標準品以EI-MS偵測的選擇質量層析圖------------------- 38
圖4-2 NPnEO標準品之EI-MS選擇質量層析圖---------------------- 39
圖4-3 真實水樣中NPnEO之EI-MS選擇質量層析圖------------------ 39
圖4-4 丙酯化-NP1EC標準品EI-MS選擇質量層析圖----------------- 40
圖4-5 丙酯化-NP1EC標準品之EI質譜圖-------------------------- 41
圖4-6 真實水樣中丙酯化-NPnEC之EI-MS選擇質量層析圖----------- 42
圖4-7 真實水樣中丙酯化-NP2EC之EI質譜圖---------------------- 43
圖4-8 壬基苯酚羧酸類化合物化合物代謝物CNPnEC之結構----------- 44
圖4-9 真實水樣中丙酯化-CNPnEC之EI-MS選擇質量層析圖---------- 45
圖4-10(a) 真實水樣中丙酯化-C7-CNP1EC之EI質譜圖-------------- 46
圖4-10(b) 真實水樣中丙酯化-C9-CNP1EC之EI質譜圖-------------- 46
圖4-10(c) 真實水樣中丙酯化-C7-CNP2EC之EI質譜圖-------------- 47
圖4-10(d) 真實水樣中,丙酯化-C9-CNP2EC之EI質譜圖------------ 47
圖4-11 逆相層析管柱分離所得之層析圖------------------------- 48
圖4-12 純化後C7-CNPnEC之EI-MS選擇質量層析圖----------------- 49
圖4-13 純化後丙酯化-C7-CNP1EC之EI質譜圖--------------------- 50
圖4-14 C7-CNP1EC之可能結構分子式---------------------------- 51
圖4-15 純化後丙酯化-C7-CNP2EC之EI質譜圖--------------------- 52
圖4-16 C7-CNP2EC之可能結構---------------------------------- 53
圖4-17 純化後C9-CNPnEC之EI-MS選擇質量層析圖----------------- 53
圖4-18 純化後丙酯化-C9-CNP1EC之EI質譜圖--------------------- 54
圖4-19 純化後丙酯化-C9-CNP2EC之EI質譜圖--------------------- 55
圖4-20 NP標準品之檢量線------------------------------------- 57
圖4-21 丙酯化-NP1EC標準品之檢量線--------------------------- 58
圖4-22 各河系中NP、NPnEC及CNPnEC的濃度比例------------------ 63
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指導教授 丁望賢(Wang-Hsien Ding) 審核日期 2001-6-28
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