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

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姓名

陳建良(Chien-Liang Chen) 查詢紙本館藏

畢業系所

化學學系

論文名稱

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
(Rapid determination of Dechlorane Plus and Dechloranes in biota samples by matrix solid-phase dispersion and gas chromatography – electron-capture negative ion mass spectrometry)

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摘要(中)

氯化耐燃劑(如Dechlorane Plus, Dechlorane 602, Dechlorane 603 及 Dechlorane 604)，已經被使用了很長一段時間，主要是為了取代具有急毒性的滅蟻靈(Mirex)。當開始使用時並沒有注意到排放到環境中的Dechlorane Plus和其相關化合物具有生物累積性和生物放大的特性。直到2006年，才於文獻中第一次被報導出，這類氯化耐燃劑具有持久性和非常高的親脂性(log KOW>9)，因此在食物鏈中累積，其殘留濃度也常在水產中被檢測到。
本篇研究主要是發展一套簡單、有效率，可快速檢測這五種氯化耐燃劑的樣品前處理方法，以便應用在不同種類生物樣品中進行萃取。使用基質固相分散萃取法(Matrix solid-phase dispersion, MSPD)來做樣品前處理，並利用氣相層析質譜儀結合電子捕捉負離子化學游離法(GC-ECNI-MS)進行偵測。從生物樣品中萃取目標待測物，並把會影響萃取效率的實驗參數，利用實驗設計法中的Box-Behnken design來進行最佳化。最佳化的實驗條件為，把1 g經由冷凍乾燥的生物樣品和2 g的SiO2，放入振盪器中快速均勻混合。把混合物轉移到含有1 g矽酸鎂的玻璃管柱中，利用矽酸鎂作為共吸附劑和淨化的作用，並用20 mL的正己烷進行沖提。再將萃取液旋濃至1 mL並定溶。回溶後取1 μL萃取液利用GC-ECNI-MS進行偵測，偵測極限可低至0.6 - 2 pg/g。實驗結果初步顯示，在各種水生樣品中都有檢測到微量的四種氯化耐燃劑。

摘要(英)

Dechlorane Plus, Dechlorane 602, Dechlorane 603 and Dechlorane 604 are chlorinated flame retardants that have been widely used as the substitution for mirex, but they have not been noticed as environmental contaminants until 2006. Regardless of their large molecular size and very high lipophilicity (log KOW > 9), Dechlorane Plus and related compounds have been detected in various aquatic and terrestrial species, supporting their bioaccumulation and biomagnification.
A simple and effective method for the rapid analysis of five chlorinated flame retardants in various biota sample is described. The method involves the use of matrix solid-phase dispersion (MSPD) prior to their determination by gas chromatography – electron-capture negative ion mass spectrometry (GC-ECNI-MS) operating in the selected-ion-monitoring (SIM) mode. The parameters affecting the extraction efficiency of the target analytes from biota sample were optimized using a Box-Behnken design method. The optimal extraction conditions involved dispersing of freeze-dried biota sample (1 g) with 2 g of silica gel in a glass tube by a vigorous shaking (1.0 min) to obtain a dry homogenous mixture. This mixture was transferred to a glass column containing 1 g of Florisil, as the clean-up co-sorbent. The target analytes were then eluted with 20 mL of n-hexane. The extract was adjusted to 1 μL and then determined by GC-ECNI-MS. The limits of detection (LODs) were 0.6 − 2 pg/g. A preliminary result revealed that trace levels of chlorinated flame retardants were detected in various biota samples.

關鍵字(中)

★ 氯化耐燃劑
★ 基質固相分散萃取法
★ 氣相層析儀
★ 電子捕捉負離子化學游離法
★ 質譜儀
★ 生物樣品

關鍵字(英)

★ Dechlorane Plus
★ matrix solid-phase dispersion
★ gas chromatography
★ electron-capture negative ion
★ mass spectrometry
★ biota samples

論文目次

目錄
中文摘要 I
英文摘要 III
謝誌 V
目錄 VII
圖目錄 IX
表目錄 XIII
第一章　前言 1
1-1　研究緣起 1
1-2　研究目標 8
第二章　文獻回顧 11
2-1　耐燃劑 11
2-1-1　耐燃劑簡介與原理 11
2-1-2　耐燃劑之分類 13
2-1-3　氯化耐燃劑簡介 16
2-2　Dechlorane plus 17
2-2-1　Dechlorane plus簡介 17
2-2-2　Dechlorane plus 性質 22
2-2-3　Dechlorane plus 毒性 25
2-2-4　Dechlorane plus 檢測的相關研究 27
2-3　基質固相分散萃取法 32
2-3-1　固態樣品萃取法簡介 32
2-3-2　基質固相分散萃取法原理 34
2-4　氣相層析質譜儀 37
2-4-1　氣相層析質譜儀簡介 37
2-4-2　電子捕捉負離子化學游離法 39
2-4-3　四極矩質譜儀 41
2-4-4　選擇離子偵測法 43
2-5　實驗設計法 44
2-5-1　實驗設計法簡介 44
2-5-2　變異數分析 46
2-5-3　反應曲面法 49
2-5-4　Box-Behnken Design 51
2-6　Mandel test 53
2-6-1　Mandel test 53
2-6-2　The Lack-of-Fit Test 55
2-6-3　基質效應 57
第三章　實驗步驟與樣品分析 61
3-1　實驗藥品與設備 61
3-1-1　實驗藥品 61
3-1-2　儀器設備 64
3-2　實驗步驟 65
3-2-1　標準品的配製 65
3-2-2　氣相層析質譜儀的參數設定 66
3-2-3　MSPD裝置示意圖 69
3-2-4　基質固相分萃取法萃取步驟 70
3-2-5　索式萃取法步驟 71
3-3　生物檢體採集 72
第四章　結果與討論 73
4-1　Dechlorane plus化合物的檢測 73
4-1-1　電子捕捉負離子化學游離法 73
4-1-2　偵測極限和檢量線 78
4-2　基質固相分散萃取法最佳化條件探討 80
4-2-1　萃取溶劑和吸附劑材質選擇 80
4-2-2　Box-Behnken design基質固相分散萃取法最佳化 83
4-3　Mandel test 與 Matrix effect 93
4-3-1　Mandel test 93
4-3-2　The Lack-of-fit test 94
4-3-3　Matrix effect 95
4-4　生物樣品檢驗 97
4-4-1　市售水產生物樣品檢驗 97
4-4-2　環境中水產生物樣品檢驗 103
4-5 檢測方法比較 112
第五章　結論與建議 117
5-1　結論 117
5-2　建議 118
第六章　參考文獻 119
附錄 127

參考文獻

參考文獻
 行政院消防署：101年全國火災統計分析，2012。
 邱增盛:RoHS指令對難燃技術的影響，高分子工業，136，2008，78-83。
 林烈利：新型磷-矽難燃劑之協同作用對環氧樹脂難燃性質之研究，專題研究計畫成果報告，正修科技大學化工與材料工程系，2010。
 陳家揚:液相層析/質譜儀的基質效應與因應之道，Chemistry，2007，第二期，第六十五卷，151-155。
 黃嫚君：以高通量微波輔助萃取法結合分散微固相萃取法快速檢測肉類產品中之亞硝胺含量研究，碩士論文，國立中央大學化學研究所，2012。
 黎正中、陳源樹:實驗設計與分析，高立圖書有限公司，2006。
 蔣安國、蔣安仁、丁敬哲、鍾健平: 以模擬技術和統計方法建構專案排程之可靠度，第一屆管理與決學術研討會特刊，2005，119-130。
 鍾尹如：以質譜技術對環境中多溴聯苯醚檢測之方法開發與應用，碩士論文，國立中央大學化學研究所，2006。
 Agency for Toxic Substances and Disease Registry., Mirex and chlordecone. Division of Toxicology and Human Health Sciences (proposed) Atlanta, 1996, GA 30333.
 Barker, S.A.; Long, A.R.; Short, C.R., Isolation of drug residues from tissues by solid phase dispersion. J. Chromatogr. A., 1989, 475, 353–361.
 Barker, S.A., Matrix solid-phase dispersion Review. J. Chromatogr. A., 2000, 885, 115–127.
 Betts, K.S., A new flame retardant in the air. Environ. Sci. Technol., 2006, 40, 1090–1091.
 Beyer, A.; Biziuk, M., Applications of sample preparation techniques in the analysis of pesticides and PCBs in food. Food. Chemistry., 2008, 108, 669–680.
 Brock, W.J.; Schroeder, R.E.; McKnight, C.A.; Vansteenhouse, J.L.; Nyberg, J.M., Oral Repeat Dose and Reproductive Toxicity of the Chlorinated Flame Retardant Dechlorane Plus. Int. J. Toxicol., 2010, 29, 582–593.
 Capriotti, A.L.; Cavaliere, C.; Giansanti, P.; Gubbiotti, R.; Samperi, R.; Laganà, A., Recent developments in matrix solid-phase dispersion extraction Review. J. Chromatogr. A., 2010, 1217, 2521–2532.
 Crump, D.; Chiu, S.; Gauthier, L.T.; Hicky, N.J.; Letcher, R.J.; Kennedy, S.W., The effects of Dechlorane Plus on toxicity and mRNA expression in chicken embryos: A comparison of in vitro and in ovo approaches. Comp. Biochem. Physiol. C., 2011, 154, 129–134.
 De la Torre, A.; Sverko, E.; Alaee, M.; Martínez, M.A., Concentrations and sources of Dechlorane Plus in sewage sludge. Chemosphere., 2011, 82, 692–697.
 Gauthier, L.T.; Hebert, C.E.; Weseloh, D.V.C., Current-Use Flame Retardants in the Eggs of Herring Gulls (Larus argentatus) from the Laurentian Great Lakes. Environ. Sci. Technol., 2007, 41, 4561–4567.
 Guerra, P.; Fernie, K.; Jimenez, B.; Pacepavicius, G.; Shen, L.; Reiner, E.; Eljarrat, E.; Barceló, D.; Alaee, M., Dechlorane Plus and Related Compounds in Peregrine Falcon (Falco peregrinus) Eggs from Canada and Spain. Environ. Sci. Technol., 2011, 45, 1284–1290.
 Hoh, E.; Zhu, L.; Hites, R.A., Dechlorane Plus, a Chlorinated Flame Retardant, in the Great Lakes. Environ. Sci. Technol., 2006, 40, 1184–1189.
 Jia, H; Sun, Y.; Liu, X.; Yang, M.; Wang, D.; Qi, H.; Shen, L.; Sverko, E.; Reiner, E.J.; Li, Y.F., Concentration and Bioaccumulation of Dechlorane Compounds in Coastal Environment of Northern China. Environ. Sci. Technol., 2011, 45, 2613–2618.
 Kakimoto, K.; Nagayoshi, H.; Yoshida, J.; Akutsu, K.; Konishi, Y.; Toriba, A.; Hayakawa, K., Detection of Dechlorane Plus and brominated flame retardants in marketed fish in Japan. Chemosphere., 2012, 89, 416–419.
 Kang, J.H.; Kim, J.C.; Jin, G.Z.; Park, H.; Baek, S.Y.; Chang, Y.S., Detection of Dechlorane Plus in fish from urban-industrial rivers. Chemosphere., 2010, 79, 850–854.
 Klosterhaus, S.L.; Stapleton, H.M.; Guardia, M.J.L.; Greig, D.J., Brominated and chlorinated flame retardants in San Francisco Bay sediments and wildlife. Environment. International., 2012, 47, 56–65.
 Möller, A.; Xie, Z.; Sturm, R.; Eibinghaus, R., Large-Scale Distribution of Dechlorane Plus in Air and Seawater from the Arctic to Antarctica. Environ. Sci. Technol., 2010, 44, 8977–8982.
 Muñoz-Arnanz, J.; Saez, M.; Hiraldo, F.; Baos, R.; Pacepavicius, G.; Alaee, M.; Jimenez, B., Dechlorane plus and possible degradation products in white stork eggs from Spain. Environ. Int., 2011, 37, 1164–1168.
 Ren, G.; Yu, Z.; Ma, S.; Li, H.; Peng, P.; Sheng, G.; Fu, J., Determination of Dechlorane Plus in Serum from Electronics Dismantling Workers in South China. Environ. Sci. Technol., 2009, 43, 9453–9457.
 Shen, L.; Reiner, E.J.; Macpherson, K.A.; Kolic, T.M.; Sverko, E.; Helm, P.A.; Bhavsar, S.P.; Brindle, I.D.; Marvin, C.H., Identification and Screening Analysis of Halogenated Norbornene Flame Retardants in the Laurentian Great Lakes: Dechloranes 602, 603, and 604. Environ. Sci. Technol., 2010, 44, 760–766.
 Shen, L.; Reiner, E.J.; Helm, P.A.; Marvin, C.H.; Hill, B.; Zhang, X.; Macpherson, K.A.; Kolic, T.M.; Tomy, T.; Brindle, I.D., Historic Trends of Dechloranes 602, 603, 604, Dechlorane Plus and Other Norbornene Derivatives and Their Bioaccumulation Potential in Lake Ontario. Environ. Sci. Technol., 2011, 45, 3333–3340.
 Siddique, S.; Xian, Q.; Abdelouahab, N.; Takser, L.; Philipps, S.P.; Feng, Y.L.; Wang, B.; Zhu, J., Levels of dechlorane plus and polybrominated diphenylethers in human milk in two Canadian cities. Environ. Int., 2012, 39, 50–55.
 Su, R.; Wang, X.; Xu, X.; Wang, Z.; Li, D.; Zhao, X.; Li, X.; Zhang, H.; Yu, A., Application of multiwall carbon nanotubes-based matrix solid phase dispersion extraction for determination of hormones in butter by gas chromatography mass spectrometry. J. Chromatogr. A., 2011, 1218, 5047–5054.
 Sverko, E.; Tomy, G.T.; Marvin, C.H.; Zaruk, D.; Reiner, E.; Helm, P.A.; Hill, B.; McCarry, B.E., Dechlorane Plus Levels in Sediment of the Lower Great Lakes. Environ. Sci. Technol., 2008, 42, 361–366.
 Sverko, E.; Reiner, E.J.; Tomy, G.T.; MccRindle, R.; Shen, L.; Arsenault, G.; Zaruk, D.; Macpherson, K.; Marvin, C.H.; Helm, P.A.; Mccarry, B.E., Compounds Structurally Related to Dechlorane Plus in Sediment and Biota from Lake Ontario (Canada). Environ. Sci. Technol., 2010, 44, 574–579.
 Sverko, E., Determination of Dechlorane Plus in the environment. PhD thesis, McMaster University., 2011.
 Sverko, E.; Tomy, G.T.; Reiner, E.J.; Li, Y.F.; McCarry, B.E.; Arnot, J.A.; Law, R.J.; Hites, R.A., Dechlorane Plus and Related Compounds in the Environment: A Review. Environ. Sci. Technol., 2011, 45, 5088–5098.
 Tomy, G.T.; Pleskach, K.; Ismail, N.; Whittle, D.M.; Helm, P.A.; Sverko, E.; Zaruk, D.; Marvin, C.H., Isomers of Dechlorane Plus in Lake Winnipeg and Lake Ontario Food Webs. Environ. Sci. Technol., 2007, 41, 2249–2254.
 US EPA., IUCLID data set for Dechlorane Plus. US. EPA., 2009.
 Van Esch, G.J., Tetrabromobisphenol A and Derivatives, WHO/IPCS, 1995.
 Van Leeuwen, S.P.J.; De Boer, J., Advances in the gas chromatographic determination of persistent organic pollutants in the aquatic environment Review. J. Chromatogr. A., 2008, 1186, 161–182.
 Vernier, M.; Wierda, M.; Bowerman, W.W.; Hites, R.A., Flame retardants and organochlorine pollutants in bald eagle plasma from the Great Lakes region. Chemosphere., 2010, 80, 1234–1240.
 Wang, D.G.; Yang, M.; Qi, H.; Sverko, E.; Ma, W.L.; Li, Y.F.; Alaee, M.; Reiner, E.J.; Shen, L., An Asia-Specific Source of Dechlorane Plus: Concentration,Isomer Profiles, and Other Related Compounds. Environ. Sci. Technol., 2010, 44, 6608–6613.
 Wu, J.P.; Zhang, Y.; Luo, X.J.; Wang, J.; Chen, S.J.; Guan, Y.T.; Mai, B.X., Isomer-Specific Bioaccumulation and Trophic Transfer of Dechlorane Plus in the Freshwater Food Web from a Highly Contaminated Site, South China. Environ. Sci. Technol., 2010, 44, 606–611.
 Zeller, H. and Kirsch, P., Hexabromocyclododecane: 28-day feeding trials with rats. Letter from BASF, EPA/OTS Doc #86-900000376, 1969.
 Zhang, X.L.; Luo, X.J.; Liu, H.Y.; Yu, L.H.; Chen, S.J.; Mai, BX., Bioaccumulation of Several Brominated Flame Retardants and Dechlorane Plus in Waterbirds from an E-Waste Recycling Region in South China: Associated with Trophic Level and Diet Sources. Environ. Sci. Technol., 2011, 45, 400–405.
 Zhao, Y.; Wang, J.; Luan, Z.; Peng, X.; Liang, Z.; Shi, L., Removal of phosphate from aqueous solution by red mud using a factorial design. J. Hazardous Mater., 2009, 165, 1193–1199.
 Zheng, J.; Wang, J.; Luo, X.J.; Tian, M.; He, L.Y.; Yuan, J.G.; Mai, B.X.; Yang, Z.Y., Dechlorane Plus in Human Hair from an E-Waste Recycling Area in South China: Comparison with Dust. Environ. Sci. Technol., 2010, 44, 9298–9303.
 Zhu, J.; Feng, Y.L.; Shoeib, M., Detection of Dechlorane Plus in Residential Indoor Dust in the City of Ottawa, Canada. Environ. Sci. Technol., 2007, 41, 7694–7698.

指導教授

丁望賢(Wang-Hsien Ding)

審核日期

2013-7-2

推文