博碩士論文 92223029 詳細資訊


姓名 楊登凱(Teng-Kai Yang)  查詢紙本館藏   畢業系所 化學學系
論文名稱 以氣相層析質譜儀檢測具荷爾蒙效應添加劑之方法開發與研究
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摘要(中) 塑膠添加劑為塑膠製品在製造、成型時,為改善原料樹脂之性能品質、賦與某些特性、維持成型品之長期品質安定或改進加工性等,而不得不添加之化學物質。一般常見有三壬苯基亞磷酸酯 ( Tris(nonylphenyl) phosphite, TNPP)類的抗氧化劑及溴化耐燃劑(brominated flame retardants, BFRs)。但由於此類物質其降解產物或是其本身結構與部分荷爾蒙類似,若進入動物體將會干擾內分泌之正常生理作用,進而影響健康,因此此類物質受到各國之高度重視,並加以規範或禁止。因此本研究主要目的就是開發一套穩定且可靠檢測烷基酚類及溴化耐燃劑的微量檢驗技術,以測定新鮮蔬果及河水中此類環境荷爾蒙之殘留量。
本研究之前處理方法為利用蒸氣蒸餾萃取方式,藉由調整不同pH及氯化鈉濃度等條件,找出最佳萃取條件,再結合氣相層析質譜儀(GC/MS)選擇離子偵測模式(selected ion monitoring, SIM)作定性定量鑑定,得到其方法偵測極限低於0.2 ng/g,分析物之標準偏差介於1.0-9.8%,回收率也都在64%以上,而烷基酚類殘留物於新鮮蔬果中之檢驗結果?NP和OP濃度為n.d.-16 ng/g及n.d.-4.8 ng/g,NP1EO及OP1EO皆低於定量極限,說明本套檢驗技術能有效檢驗食品之烷基酚類殘留物之目的,且由於這些蔬果食品中皆能測出這些環境荷爾蒙
之殘存,値得國人在蔬果食品中之攝食高度重視與關心。
另一部份為開發固相萃取方式萃取水樣中之溴化耐燃劑TBBPA及HBCD,並比較不同萃取管柱之萃取效率,其中以新開發之聚合填充物Oasis HLB固相萃取管柱具有最佳的萃取回收率,而結合氣相層析質譜儀(GC/MS)選擇離子偵測模式(selected ion monitoring, SIM)作定性定量鑑定,得到其方法偵測極限低於20 ng/L,分析物之標準偏差介於3.6-14 %,回收率也都在79%以上,且於台灣河水樣品中之檢驗結果發現HBCD濃度為73 ng/L–581 ng/L,TBBPA則低於定量極限,說明本套檢驗技術能有效檢驗水樣之溴化耐燃劑之目的。且由於這些河水樣品中皆能測出這些環境荷爾蒙之殘存,値得國人對河川中溴化耐燃劑之污染高度重視與關心。
摘要(英) The chemical additives are needed for the plastic products manufacturing and takes shape, to improve their performance of quality, characteristics, stability, and workability. Tris(nonylphenyl)phosphite (TNPP) and brominated flame retardants (BFRs) are two common chemical additives with large and global industrial use. The presence of endocrine-disrupting residues in the environment or food has raised increasing concern about their impact on wildlife and human health. This research is to develop stable methods to determine alkylphenol compounds in fresh fruits and vegetables, and two common used BFRs in river water samples.
The first study describes a simple and sensitive method for determining the 4-tert.-octylphenol (4-t-OP), 4-nonylphenol isomers (4-NPs), and their monoethoxylates (4-t-OP1EO and 4-NP1EOs), in fresh fruits and vegetables. The method involves extracting a sample by a modified Nielson-Kryger steam distillation extraction using n-hexane for one hour. The alkylphenolic compounds were identified and quantitated by gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring (SIM) mode. The quantitation limit of this method was less than 0.2 ng/g in 10 g (fresh weight) of sample. Recovery of these compounds in spiked samples exceeded 64% while RSD ranged from 1.0 to 9.8%. Alkylphenolic residues were detected in fresh fruits and vegetables at concentrations of 4-NPs and 4-t-OP from n.d. to 16 ng/g and from n.d. to 4.8 ng/g (fresh weight), respectively. NP1EO and OP1EO were always below the quantitation limit.
Another study presents a modified method to analyze two common BFRs, tetrabromobisphenol A (TBBPA) and hexabromocyclodecane (HBCD) in water samples. The newly developed Oasis HLB solid-phase extraction cartridge provides the optimal sample extraction results. The analytes were then identified and quantitatively determined by gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring (SIM) mode. The limits of quantitation of these compounds were less than 20 ng/L in 250 mL water sample. Recovery of these two BFRs in spiked samples exceeded 79% while RSD ranged from 3.6 to 14%. BFRs were detected in water samples at concentrations of HBCD from 73 to 581 ng/L. TBBPA was below the quantitation limit.
關鍵字(中) ★ 固相萃取法
★ 蒸氣蒸餾萃取法
★ 溴化耐燃劑
★ 烷基酚類
★ 氣相層析質譜儀
★ 荷爾蒙效應
關鍵字(英) ★ solid-phase extraction
★ steam distillation extraction
★ brominated flame retardants
★ alkylphenol compounds
★ endocrine-disrupting
★ GC/MS
論文目次 目錄
中文摘要------------------------------------------------------------------ Ⅰ
英文摘要------------------------------------------------------------------ Ⅲ
目錄---------------------------------------------------------------------- Ⅴ
表目錄-------------------------------------------------------------------- Ⅸ
圖目錄-------------------------------------------------------------------- XI
第一章 前言---------------------------------------------------------------- 1
1-1 研究緣起---------------------------------------------------------- 1
1-2 研究目標---------------------------------------------------------- 11
第二章 文獻探討------------------------------------------------------------ 13
2-1 塑膠添加劑----------------------------------------------------------- 13
2-1-1 塑膠抗氧化劑------------------------------------------------ 14
2-1-2 塑膠耐燃劑--------------------------------------------------- 15
2-2 內分泌干擾物質----------------------------------------------------- 16
2-2-1內分泌干擾物質之簡介------------------------------------- 16
2-2-2 烷基酚類化合物之荷爾蒙效應及毒性------------------ 20
2-2-3 溴化耐燃劑之荷爾蒙效應及毒性------------------------ 21
2-3 國內外相關研究----------------------------------------------------- 22
2-3-1烷基酚類化合物之相關文獻-------------------------------- 22
2-3-2 溴化耐燃劑之相關文獻------------------------------------- 26
2-4 蒸氣蒸餾萃取法----------------------------------------------------- 29
2-5 固相萃取法----------------------------------------------------------- 31
2-6 氣相層析質譜儀----------------------------------------------------- 34
2-6-1 四極矩質譜儀----------------------------------------------- 34
2-6-2 選擇離子偵測法-------------------------------------------- 35
第三章 實驗步驟與樣品分析--------------------------------------------- 37
3-1 實驗藥品與儀器設備----------------------------------------------- 37
3-1-1 實驗藥品------------------------------------------------------ 37
3-1-2 儀器設備------------------------------------------------------ 39
3-2 實驗步驟------------------------------------------------------------ 40
3-2-1 烷基酚類化合物之分析------------------------------------ 40
3-2-1-1 標準品製備-------------------------------------------- 40
3-2-1-2 氣相層析質譜儀參數設定-------------------------- 41
3-2-1-3 蔬果樣品之蒸汽蒸餾萃取步驟-------------------- 43
3-2-1-4 蔬果樣品之蒸氣蒸餾萃取回收率實驗----------- 43
3-2-1-5 塑膠樣品溶出測試之固相萃取步驟-------------- 44
3-2-2 溴化耐燃劑之分析---------------------------------------- 45
3-2-2-1 標準品製備------------------------------------------ 45
3-2-2-2 氣相層析質譜儀參數設定------------------------ 45
3-2-2-3 真實水樣固相萃取步驟--------------------------- 47
3-2-2-4 真實水樣之固相萃取回收率實驗--------------- 47
第四章 結果與討論--------------------------------------------------------- 48
4-1 烷基酚類化合物----------------------------------------------------- 48
4-1-1 烷基酚類化合物之測定------------------------------------ 48
4-1-2 檢量線--------------------------------------------------------- 50
4-1-3 蒸氣蒸餾萃取前處理法最佳條件探討------------------ 51
4-1-4 蒸氣蒸餾萃取前處理方法探討--------------------------- 53
4-1-5 市售新鮮蔬果的烷基酚類化合物分析結果------------ 54
4-1-6 市售不同包裝果菜汁的烷基酚類化合物殘留比較--- 58
4-1-7 市售不同材料之塑膠包裝容器的烷基酚類化合物溶出實驗------------ 59
4-1-8 我國與德國檢測結果比較--------------------------------- 61
4-2 溴化耐燃劑----------------------------------------------------------- 62
4-2-1溴化耐燃劑之測定------------------------------------------ 62
4-2-2 檢量線-------------------------------------------------------- 65
4-2-3 找尋最適合的固相萃取管柱------------------------------ 65
4-2-4 固相萃取前處理方法探討--------------------------------- 68
4-2-5 台灣河流中的溴化耐燃劑分析結果--------------------- 68
第五章 結果與建議--------------------------------------------------------- 73
5-1 結論---------------------------------------------------------------- 73
5-2 建議--------------------------------------------------------- 74
第六章 參考文獻------------------------------------------------------------ 75
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指導教授 丁望賢(Wang-Hsien Ding) 審核日期 2005-6-20
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