以微波輔助萃取搭配氣相層析質譜儀檢測底泥樣品中有機磷耐燃劑之研究

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研究生：	鍾孝武 Siao-Wu Jhong
論文名稱：	以微波輔助萃取搭配氣相層析質譜儀檢測底泥樣品中有機磷耐燃劑之研究 Determination of Organophosphate Flame retardants in Sediment by Microwave-Assisted Extraction and Gas Chromatography Mass Spectrometry
指導教授：	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：	97
語文別：	中文
論文頁數：	107
中文關鍵詞：	氣相層析質譜儀、微波輔助萃取、氣相層析儀、耐燃劑、有機磷耐燃劑
外文關鍵詞：	GC-MS, GC, Gas Chromatography Mass Spectrometry, MAE, OPFR, Flame retardants, Microwave-Assisted Extraction, Organophosphate Flame retardants
相關次數：	點閱：13 下載：0
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有機磷耐燃劑(Organophosphate flame retardants, OPFRs)被廣泛的用於各種材料之中，如：PVC塑料、PU塑料、油漆塗料、壁紙、紡織品、電子產品等。在2004年全世界的有機磷耐燃劑用量達30萬噸以上。相較於溴系耐燃劑(如：Polybrominated diphenyl ethers，PBDEs、Hexabromocyclododecane，HBCDs)，有機磷耐燃劑具有較佳的水溶性，因此其被認為更具有移動性，較容易藉由水路徑而進入到環境之中。有機磷耐燃劑相較於溴系耐燃劑被認為其毒性較低，同時對環境的傷害也較小。但部分有機磷耐燃劑，如三-(2-氯乙基)磷酸酯{Tris-(2-chloroethyl)phosphate, TCEP}被國際癌症研究機構(International Agency for Research on Cancer, IARC)判定為第三類的致癌物(Group 3 carcinogen)。因有機磷耐燃劑如此廣泛的被使用於生活之中，故我們有所必要發展一個快速且便利的方法以偵測環境中的有機磷耐燃劑。
本研究發展了一個以微波輔助萃取(microwave-assisted extraction,MAE)結合氣相層析質譜儀(GC-MS)偵測底泥樣品中五種常用有機磷耐燃劑的檢測方法。於此將有機磷耐燃劑運用微波輔助萃取的各項參數(如：萃取溶劑種類與體積、萃取溫度、萃取時間等)，作一系統性的研究並將參數最佳化。微波輔助萃取法所得之最佳化實驗參數如下，以40 mL的丙酮作為萃取溶劑，在120℃下對2 g的底泥樣品進行20分鐘的萃取。後利用HLB固相萃取管柱與氧化鋁以淨化萃取液。本實驗的定量極限(limits of quantification, LOQ)可達100-250 pg/g(乾重)。除利用GC-EI-MS以選擇離子偵測模式定量外，並利用GC-CI-MS以定性。本實驗的萃取回收率在60-106%之間，相對標準偏差在1-11%之間。與文獻中的其他萃取方法相較之下，本實驗有著更良好的結果。最後將本方法應用於真實底泥樣品中，各樣品的有機磷耐燃劑總濃度介於9-13 ng/g之間。

Organophosphate flame retardants (OPFRs) have been used widely in a large variety of materials, such as PVC plastics, polyurethane foams, paints, wall papers, textiles, and electronic equipment, etc. In 2004, more than
300,000 tons of OPFRs were used worldwide. Because OPFRs were more water-soluble than the brominated flame retardants (i.e., Polybrominated diphenyl ethers, PBDEs or Hexabromocyclododecane, HBCDs), OPFRs are assessed to be more mobile, so they are easier into environment by aquatic
pathway. They are considered less toxicity and less harm to environment than brominated flame retardants, however, some OPFRs, such as TCEP, were classified by IARC as a Group 3 carcinogen. The widespread use of OPFRs and increasing public concern stimulated our interest in developing a rapid
and reliable method for determining their presence and fate in aquatic environments.
In this study, a microwave-assisted extraction (MAE) method coupled with gas chromatography-mass spectrometry (GC-MS) to determine five commonly used organophosphate flame retardants in sediment was presented. Parameters such as type and volume of extraction solvent, extraction
temperature, time for the quantitative extraction of OPFRs by MAE were optimized. The OPFRs can be completely extracted by 40 mL acetone at 120 °C with 20 min of extraction from 2 g sediment sample. HLB-SPE coupled with aluminium oxide was employed to cleanup the extract. Limits
of quantification (LOQs) were established between 100 to 250 pg/g (dry weight) for 2 g sediment sample. Moreover, GC-MS with chemical ionization was used to confirm the identification of the analytes. Recovery of OPFRs in spiked sediment samples ranged from 60% to 106% with 1-11% RSD. The results obtained using this approach is better than that from the previous reported methods. This developed method was finally applied to real sediment samples, a preliminary result shows that their total concentrations were ranging from 9 to 13 ng/g.

中文摘要.........................................................................................................Ⅰ
英文摘要.........................................................................................................Ⅲ
謝誌.................................................................................................................Ⅴ
目錄.................................................................................................................Ⅵ
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 耐燃劑簡介.........................................................................................7
2-2 有機磷耐燃劑...................................................................................12
2-2-1 有機磷耐燃劑簡介....................................................................12
2-2-2 有機磷耐燃劑之性質................................................................14
2-2-3 有機磷耐燃劑之毒性................................................................15
2-2-4 有機磷耐燃劑的相關研究........................................................21
2-3 微波輔助萃取法...............................................................................27
2-3-1 微波簡介....................................................................................27
2-3-2 微波加熱原理............................................................................28
2-3-3 微波輔助萃取裝置....................................................................32
2-3-4 微波輔助於萃取之應用............................................................34
2-4 氣相層析質譜儀...............................................................................36
2-4-1 四極矩式質量分析器................................................................38
2-4-2 離子阱式質量分析器................................................................40
2-4-3 化學游離法................................................................................42
第三章  實驗步驟與樣品分析.....................................................................45
3-1 實驗藥品與儀器設備.......................................................................45
3-1-1 實驗藥品....................................................................................45
3-1-2 儀器設備....................................................................................47
3-2 實驗步驟...........................................................................................48
3-2-1 標準品的配製............................................................................48
3-2-2 層析分離....................................................................................49
3-2-3 實驗步驟....................................................................................53
3-2-4 真實樣品的萃取與淨化............................................................54
3-2-5 真實樣品之萃取回收率實驗....................................................55
3-3 底泥樣品採集..................................................................................56
第四章  結果與討論....................................................................................57
4-1	氣相層析質譜儀對有機磷耐燃劑之分析.......................................57
4-1-1 以電子撞擊游離法偵測有機磷耐燃劑標準品........................57
4-1-2 以化學游離法偵測有機磷耐燃劑標準品................................62
4-1-3 檢量線........................................................................................67
4-2 微波輔助萃取條件之最佳化...........................................................68
4-2-1 萃取溶劑對回收率之影響........................................................68
4-2-2 萃取溶劑量對回收率之影響....................................................70
4-2-3 萃取溫度對回收率之影響........................................................72
4-2-4 萃取時間對回收率之影響........................................................74
4-3 樣品淨化步驟...................................................................................76
4-4 氣相層析質譜儀對底泥樣品中有機磷耐燃劑之分析...................78
4-4-1 添加待測物之底泥樣品中有機磷耐燃劑之測定....................78
4-4-2 真實樣品中有機磷耐燃劑之測定............................................85
4-5 與其他文獻結果之比較...................................................................92
第五章  結論.................................................................................................95
參考文獻.........................................................................................................97

                                

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