開發基質固相分散萃取法檢測室內灰塵中的鹵系阻燃劑

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姓名

宮敏純(Min-Chen Kung) 查詢紙本館藏

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化學學系

論文名稱

開發基質固相分散萃取法檢測室內灰塵中的鹵系阻燃劑

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摘要(中)

鹵系阻燃劑如五溴酚(Pentabromophenol, PeBP)、四氯雙酚A (Tetrachlorobisphenol A, TCBPA)和四溴雙酚A (Tetrabromobisphenol A)廣泛的被添加在電器用品及生活用品中 (如:沙發、窗簾)，在使用與丟棄的過程中阻燃劑可能會釋放到環境，累積在灰塵中。各國的研究也都有發現阻燃劑在灰塵中殘留，我們因此會透過接觸或吸入灰塵，而在體內累積鹵系阻燃劑，對我們產生健康上的影響。
　　本研究主要是開發一套簡單且快速檢測這三種鹵系阻燃劑的前處理方法，可以應用在基質複雜的室內灰塵中。利用震盪輔助基質固相分散萃取法 (Vortex-homogenized matrix solid-phase dispersion, VH-MSPD) 進行樣品前處理，搭配超高效液相層析高解析串聯質譜儀(ultra-high performance liquid chromatography quadrupole time-of-flight mass spectrometer, UHPLC-QTOF-MS)進行檢測。
　　MSPD的最佳化利用實驗統計設計(Statistical experimental design) 法中的Box-Behnken design (BBD)及變異數分析(Analysis of variance, ANOVA)來做最佳化探討。最佳化的萃取條件為：取0.1 g的灰塵樣品與0.1 g矽酸鎂，放入震盪器中快速混和均勻，再將混和物放入含有0.6 g C18的玻璃管柱中，先使用6 ml的正己烷進行淨化，再加入6 ml的甲醇:乙腈=1:1(v/v)進行沖提並收集，萃取液旋濃乾燥，再以甲醇100 μL進行回溶，取3 μL進樣UHPLC-QTOF-MS進行檢測分析。偵測極限(LOD)為3-15 ng/g；Inter-days及Intra-day的測試所得相對標準偏差(RSDs)皆小於5%，顯示本方法具有良好的穩定性與再現性。在採集的室內灰塵中所測得的鹵化阻燃劑以TBBPA為主，其濃度為70-350 ng/g。

摘要(英)

Halogenated flame retardants (HFRs) such as pentabromophenol( PeBP ), tetrachlorobisphenol A( TCBPA ), and tetrabromobisphenol A are widely applied in the manufacture of household appliances, daily articles, and furnitures, e.g. sofa and drapes. Due to how common they are, HFRs can be released into the environment during use of previously mentioned items, as shown by recent studies that show HFRs residues in indoor dust. Through dermal contact or inhalation of indoor dust, we may accumulate HFRs in our bodies, which can potentially affect our health.
　　This research developed a simple and rapid method for the determination of three HFRs in complex indoor dusts. This method involved the use of vortex-homogenized matrix solid-phase dispersion (VH-MSPD) coupled with ultra-high performance liquid chromatography quadrupole time-of-flight mass spectrometer (UHPLC-QTOF-MS UHPLC-QTOF-MS).
　　The parameters of the extraction method were optimized by Box-Behnken design and the analysis of variance(ANOVA). The optimal conditions of VH-MSPD were: dispersing 0.1g indoor dust sample with 0.1g Florisil by vigorous shaking to obtain a homogenous mixture. The mixture was transferred to a glass column containing 0.6g of octadecyl bonded silica (C18), which was used as the clean-up co-sorbent along with the addition of 6 mL n-Hexane. The target analytes were then eluted with 6 mL of a mixture of methanol and acetonitrile (1:1,v/v). After rotary evaporation to dryness, the residue was re-dissolved in 100μL of methanol. A fraction of the 3μL final extract was directly injected into UHPLC-QTOF-MS system for detection.
　　The limit of detections (LODs) for these three HFRs in indoor dust samples were determined to be 3-15 ng/g. The relative standard deviations (RSDs) of inter-days and intra-day tests were lower than 5%, and the concentration of TBBPA detected in indoor dust samples ranged from 70-350 ng/g.

關鍵字(中)

★ 基質固相分散萃取法
★ 鹵系阻燃劑

關鍵字(英)

論文目次

摘要 i
Abstract iii
謝誌 v
目錄 vii
圖目錄 xi
表目錄 xiii
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　室內灰塵 5
2-2　阻燃劑 6
2-2-1　阻燃劑簡介與原理 6
2-2-2　阻燃劑之分類 7
2-3　鹵系阻燃劑 9
2-3-1　溴化阻燃劑簡介 9
2-3-2　氯化阻燃劑簡介 12
2-3-3　鹵系阻燃劑性質 13
2-3-4　鹵系阻燃劑毒性 15
2-4　國外相關研究 16
2-5　基質固相分散萃取法 20
2-5-1　基質固相分散萃取法簡介 20
2-5-2　基質固相分散萃取法原理 21
2-6　超高效液相層析高解析串聯質譜儀 23
2-6-1 Core-shell管柱 24
2-6-2四極矩飛行時間串聯式質譜儀 26
2-7　同位素內標定量法 27
第三章　實驗步驟與樣品分析 29
3-1　實驗藥品與設備 29
3-1-1　實驗藥品 29
3-1-2　儀器設備 31
3-2　實驗步驟 32
3-2-1　標準品配製 32
3-2-2　超高效液相層析串聯質譜儀參數設定 33
3-2-3　質量校正 34
3-2-4　基質固相分散萃取法實驗流程 35
3-3　灰塵採集 36
3-3-1　空白灰塵的淨化 37
3-3-2　樣品添加步驟 37
第四章　結果與討論 39
4-1　UHPLC-QTOF-MS對鹵系阻燃劑的測定 39
4-1-1　待測物的分析 39
4-1-2　檢量線與偵測極限 42
4-2　基質固相分散萃取法之最佳化探討 43
4-2-1　沖提溶劑種類選擇 43
4-2-2　分散劑種類探討 44
4-2-3　沖提溶劑體積探討 45
4-2-4　Box-Behnken Design 基質固相分散萃取法最佳化 46
4-2-5　因子間交互作用力的探討 49
4-3　Mandel test 與The Lack-of-Fit test 53
4-3-1　Mandel test 53
4-3-2　The Lack-of-Fit test 54
4-4　真實樣品之檢測 56
4-5　檢測方法的穩定性 62
4-6　方法比較 63
第五章　結論 65
第六章　參考文獻 67
附錄 73

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指導教授

丁望賢(Wang-Hsien Ding)

審核日期

2018-6-25

推文