博碩士論文 105223021 詳細資訊




以作者查詢圖書館館藏 以作者查詢臺灣博碩士 以作者查詢全國書目 勘誤回報 、線上人數:14 、訪客IP:3.236.124.56
姓名 宮敏純(Min-Chen Kung)  查詢紙本館藏   畢業系所 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
相關論文
★ 以質譜技術探討非共價鍵結蛋白質聚合物之結構★ 以液相層析質譜儀檢測水樣與生物檢體中 全氟界面活性劑之濃度
★ 利用液相層析串聯質譜技術檢測水環境中藥物殘留物之方法開發與應用★ 直鏈式烷基苯基二甲基銨鹽類陽離子型界面活性劑在水環境中微量檢測方法的研究
★ 芳香族磺酸鹽類有機污染物在水環境中的分析與研究★ 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
★ 以固相萃取法及氣相層析質譜儀對水環境中動情激素類有機污染物之分析與研究★ 利用熱裂解直接高溫衍生化法快速分析直鏈式烷基三甲基銨鹽之方法建立與探討
★ 利用感應偶合電漿質譜儀檢測半導體製程用化學品中微量金屬不純物之分析研究★ 應用毛細管電泳間接偵測方法分離四級銨鹽界面活性劑
★ 利用毛細管電泳結合線上濃縮方法分離奈磺酸鹽之機制探討★ 快速分析水環境中醫療藥品殘留物之研究與探討
★ 以毛細管電泳法與電灑游離質譜法探討內包錯合物之研究★ 以氣相及液相層析質譜儀分析具荷爾蒙效應物質之方法開發
★ 以離子配對高效液相層析儀檢測螢光增白劑在不同基質中之研究★ 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
檔案 [Endnote RIS 格式]    [Bibtex 格式]    [相關文章]   [文章引用]   [完整記錄]   [館藏目錄]   [檢視]  [下載]
  1. 本電子論文使用權限為同意立即開放。
  2. 已達開放權限電子全文僅授權使用者為學術研究之目的,進行個人非營利性質之檢索、閱讀、列印。
  3. 請遵守中華民國著作權法之相關規定,切勿任意重製、散佈、改作、轉貼、播送,以免觸法。

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
參考文獻  台灣質譜學會,質譜分析技術原理與應用,2015。
 行政院消防署,105年火災統計分析,2016。
 香港消防處,消防安全大使訓練講義6月第十一版,2008。
 陳建良,以基質固相分散萃取法快速檢測生物樣品中之氯化耐燃劑,碩士論文,國立中央大學化學研究所,2013。
 黎正中、陳源樹,實驗設計與分析,2006。
 鍾尹如,以質譜技術對環境中多溴二苯醚檢測之方法與應用,碩士論文,國立中央大學化學研究所,2006。
 Abafe, O. A.; Martincigh, B. S., Determination and human exposure assessment of polybrominated diphenyl ethers and tetrabromobisphenol A in indoor dust in South Africa. Environmental Science and Pollution Research 2008, 23:7038–7049
 Barker, S. A.; Long, A. R.; Short, C. R., Isolation of drug residues from tissues by solid phase dispersion. Journal of Chromatography 1989, 475: 353-361
 Björklund, J. A.; Thuresson, K;De Wit, C. A., Perfluoroalkyl compounds (PFCs) in indoor dust: concentrations, human exposure estimates, and sources. Environmental Science & Technology 2009,43(7):2276-81
 Blanco, E.; Casais, M. C.; Mejuto, M. C.; Cela, R., Approaches for the simultaneous extraction of tetrabromobisphenol A, tetrachlorobisphenol A, and related phenolic compounds from sewage sludge and sediment samples based on matrix solid-phase dispersion. Analytical Chemistry 2006,78(8):2772-8
 Bruins, A. P., Mechanistic aspects of electrospray ionization. Journal of Chromatography A, 1998, 794, 345- 357.
 Canesi, L. 1.; Lorusso, L. C.; Ciacci, C.; Betti, M.; Gallo, G., Effects of the brominated flame retardant tetrabromobisphenol-A (TBBPA) on cell signaling and function of Mytilus hemocytes: involvement of MAP kinases and protein kinase C. Aquatic Toxicology, 2005,75(3):277-87.
 Chu, S.; Haffner, G. D.; Letcher, R. J., Simultaneous determination of tetrabromobisphenol A, tetrachlorobisphenol A, bisphenol A and other halogenated analogues in sediment and sludge by high performance liquid chromatography-electrospray tandem mass spectrometry. Journal of Chromatography A. 2005, 1097(1-2):25-32
 Chu, S.; Letcher, R. J., Halogenated phenolic compound determination in plasma and serum by solid phase extraction, dansylation derivatization and liquid chromatography-positive electrospray ionization-tandem quadrupole mass spectrometry. Journal of Chromatography A, 2013,1320:111-7.
 D. Guillarme ;S. Fekete, Fast and Efficient HPLC Separations With Superficially Porous Particles. Analytical Pharmaceutical Chemistry.2013
 D′Hollander, W.; Roosens, L.; Covaci, A.; Cornelis, C.; Reynders, H.; Campenhout, K.V.; Voogt, P.d.; Bervoets, L., Brominated flame retardants and perfluorinated compounds in indoor dust from homes and offices in Flanders, Belgium. Chemosphere. 2010, 81(4):478-87.
 Ferreira, S. L.; Bruns, R. E.; Ferreira, H. S.; Matos, G. D.; David, J. M.; Brandão, G. C.; da Silva, E. G.; Portugal, L. A.; dos Reis, P. S.; Souza, A. S.; dos Santos, W. N., Box-Behnken design: an alternative for the optimization of analytical methods. Analytica Chimica Acta. 2007, 597(2):179-86.
 Fridén, U. E.; McLachlan, M. S.; Berger, U., Chlorinated paraffins in indoor air and dust: concentrations, congener patterns, and human exposure. Environment International. 2011, 37(7):1169-74.
 Gallart-Ayala, H.; Moyano, E.; Galceran, M. T., On-line solid phase extraction fast liquid chromatography-tandem mass spectrometry for the analysis of bisphenol A and its chlorinated derivatives in water samples. Journal of Chromatography A. 2010, 1217(21):3511-8.
 Geens, T.; Roosens, L.; Neels, H.; Covaci, A., Assessment of human exposure to Bisphenol-A, Triclosan and Tetrabromobisphenol-A through indoor dust intake in Belgium. Chemosphere. 2009, 76(6):755-60.
 Hilger, B.; Fromme, H.; Völkel, W.; Coelhan, M., Occurrence of chlorinated paraffins in house dust samples from Bavaria, Germany. Environmental Pollution . 2013, 175:16-21
 Hu, X. J.; Zhang, H. J.; Wang, X. H.; Ding, C. M.; Jin, Y. L.; Lin, S. B., Determination of bisphenolic and halogenated bisphenolic compounds in human urine by high performance liquid chromatography-tandem mass spectrometry. Chinese Journal of Analytical Chemistry. 2014,42(7), 1053-1056
 Inouye, B.; Katayama, Y.; Ishida, T.; Ogata, M.; Utsumi, K., Effects of aromatic bromine compounds on the function of biological membranes. Toxicology and Applied Pharmacology. 1979, 48(3):467-77
 Jones-Otazo, H. A.; Clarke, J. P.; Diamond, M. L.; Archbold, J. A.; Ferguson, G.; Harner, T.; Richardson, G. M.; Ryan, J. J.; Wilford, B., Is house dust the missing exposure pathway for PBDEs? An analysis of the urban fate and human exposure to PBDEs. Environmental Science & Technology. 2005, 39(14):5121-30
 Kitamura, S.; Jinno, N.; Ohta, S.; Kuroki, H.; Fujimoto, N., Thyroid hormonal activity of the flame retardants tetrabromobisphenol A and tetrachlorobisphenol A. Biochemical and Biophysical Research Communications.2002, 293(1):554-9.
 Lankova, D.; Kockovska, M.; Lacina, O.; Kalachova, K.; Pulkrabova, J.; Hajslova, J., Rapid and simple method for determination of hexabromocyclododecanes and other LC-MS-MS-amenable brominated flame retardants in fish. Analytical and Bioanalytical Chemistry. 2013, 405(24):7829-39
 Lankova, D.; Svarcova, A.; Kalachova, K.; Lacina, O.; Pulkrabova, J.; Hajslova, J., Multi-analyte method for the analysis of various organohalogen compounds in house dust. Analytica Chimica Acta. 2015, 854:61-9.
 Lewis, R.G.; Fortune, C.R.; Willis, R.D.; Camann, D.E.; Antley, J.T., Distribution of pesticides and polycyclic aromatic hydrocarbons in house dust as a function of particle size., Environmental Health Perspectives. 1999, 107(9):721-6.
 Li, Y. N.; Zhou, Q. X., Metabolic transformation and ecotoxicology of tetrabromobisphenol A: A review. Chinese Journal of Ecology 2008, 27(2), 263-268
 Maertens, R. M.; Bailey, J.; White, P. A., The mutagenic hazards of settled house dust: a review. Mutation Research. 2004, 567(2-3):401-25.
 Mascolo, G.; Locaputo, V.; Mininni, G., New perspective on the determination of flame retardants in sewage sludge by using ultrahigh pressure liquid chromatography-tandem mass spectrometry with different ion sources., Journal of Chromatography A., 2010 2;1217(27):4601-11.
 Meerts, I. A.; van Zanden, J. J.; Luijks, E. A.; van Leeuwen-Bol, I.; Marsh, G.; Jakobsson, E.; Bergman, A.; Brouwer, A., Potent competitive interactions of some brominated flame retardants and related compounds with human transthyretin in vitro. Toxicological Sciences. 2000,56(1):95-104.
 Oberg, K.; Warman, K.; Oberg, T., Distribution and levels of brominated flame retardants in sewage sludge. Chemosphere. 2002, 48(8):805-9.
 Pullen, S.; Boecker, R.; Tiegs, G., The flame retardants tetrabromobisphenol A and tetrabromobisphenol A-bisallylether suppress the induction of interleukin-2 receptor alpha chain (CD25) in murine splenocytes. Toxicology. 2003, 184(1):11-22.
 Sánchez-Brunete, C.; Miguel, E.; Tadeo, J. L., Determination of tetrabromobisphenol-A, tetrachlorobisphenol-A and bisphenol-A in soil by ultrasonic assisted extraction and gas chromatography-mass spectrometry. Journal of Chromatography A. 2009, 1216(29):5497-503.
 Song, S.; Song, M.; Zeng, L.; Wang, T.; Liu, R.; Ruan, T.; Jiang, G.. Occurrence and profiles of bisphenol analogues in municipal sewage sludge in China. Environmental Pollution. 2014, 186:14-9.
 Stapleton, H. M.; Allen, J. G.; Kelly, S. M.; Konstantinov, A.; Klosterhaus, S.; Watkins, D.; McClean, M. D.; Webster, T. F., Alternate and new brominated flame retardants detected in U.S. house dust. Environmental Science & Technology. 2008, 42(18):6910-6.
 Takigami, H.; Suzuki, G.; Hirai, Y.; Sakai, S., Brominated flame retardants and other polyhalogenated compounds in indoor air and dust from two houses in Japan. Chemosphere. 2009,76(2):270-7
 Thomsen, C.; Leknes, H.; Lundanes, E.; Becher, G., A new method for determination of halogenated flame retardants in human milk using solid-phase extraction. Journal of Analytical Toxicology. 2002, 26(3):129-37.
 Tollbäck, J.; Crescenzi, C.; Dyremark, E., Determination of the flame retardant tetrabromobisphenol A in air samples by liquid chromatography-mass spectrometry. Journal of Chromatography A 2006, 1104(1-2):106-12
 Villaverde-de-Sáa, E.; Valls-Cantenys, C.; Quintana, J. B.; Rodil, R.; Cela, R., Matrix solid-phase dispersion combined with gas chromatography-mass spectrometry for the determination of fifteen halogenated flame retardants in mollusks. Journal of Chromatography A. 2013, 1300:85-94.
 Vocadlo, D. J.; Davies, G. J.; Laine, R.; Withers, S. G., Catalysis by hen egg-white lysozyme proceeds via a covalent intermediate. Nature. 200, 412(6849):835-8.
 Wang, W.; Abualnaja, K. O.; Asimakopoulos, A. G.; Covaci, A.; Gevao, B.; Johnson-Restrepo, B.; Kumosani, T. A.; Malarvannan, G.; Minh, T. B.; Moon, H. B.; Nakata, H.; Sinha, R. K.; Kannan, K., A comparative assessment of human exposure to tetrabromobisphenol A and eight bisphenols including bisphenol A via indoor dust ingestion in twelve countries. Environment International. 2015, 83:183-91.
 Yang, Y.; Lu, L.; Zhang, J.; Yang, Y.; Wu, Y.; Shao, B., Simultaneous determination of seven bisphenols in environmental water and solid samples by liquid chromatography-electrospray tandem mass spectrometry. Journal of Chromatography A. 2014, 1328:26-34.
 Zhang, G.; Annan, R. S.; Carr, S. A.; Neubert, T. A., Overview of peptide and protein analysis by mass spectrometry. Current Protocols in Protein Science. 2010, Chapter 16:Unit16.1.
指導教授 丁望賢(Wang-Hsien Ding) 審核日期 2018-6-25
推文 facebook   plurk   twitter   funp   google   live   udn   HD   myshare   reddit   netvibes   friend   youpush   delicious   baidu   
網路書籤 Google bookmarks   del.icio.us   hemidemi   myshare   

若有論文相關問題,請聯絡國立中央大學圖書館推廣服務組 TEL:(03)422-7151轉57407,或E-mail聯絡  - 隱私權政策聲明