臺灣博碩士論文加值系統

多溴二苯醚常被添加於電子材料、紡織品及建築材料中，用為火焰阻燃劑。由於屬添加型的阻燃劑，容易釋放於生活環境中，對環境及人體都有莫大的影響。多溴二苯醚的檢測方法，傳統使用的萃取方法常需要花很長的時間及大量有機溶劑,對於分析方法的綠色需求來說不盡理想，因此發展一個新的分析技術來加以改進是重要的課題。
本研究利用微波輔助頂空固相微萃取結合氣相層析電子捕捉偵測器(GC-ECD)分析多溴二苯醚在樣品中的含量。本實驗目標分析物為BDE-28、47、99、100、153、154、183、209。在管柱選擇方面，BDE-28、47、99、100、153、154、183使用的為HP-5ms(30m,0.25mm I.D,0.25μm)毛細管管柱，BDE-209則使用長度較短且厚度較薄的DB-5ms(15m,0.25mm I.D,0.1μm)之管柱 。
實驗中使用10mL樣品量來進行最佳化條件探討，分別探討纖維塗佈材質，微波照射時間、功率，頂空採樣系統溫度及脫附時間、溫度，樣品pH及鹽類添加等最佳化條件。結果顯示，BDE-28、47、99、100、153、154、183七種多溴二苯醚，最佳化條件為使用100μm PDMS固相微萃取纖維，採樣溫度固定在10℃，以微波功率177瓦照射30分鐘，完成後，在GC注射口以300℃脫附4分鐘進行GC-ECD分析。偵測線性範圍BDE-28為O.05-5 ng/L，BDE-47、99、100、153、154為0.1-10 ng/L及BDE-183為5-500ng/ L，偵測極限為0.01-1ng/L之間，相關係數皆在0.99以上。
BDE-209(十溴二苯醚)最佳化條件為使用100μm PDMS固相微萃取纖維，冷凝溫度固定在10℃，以微波功率210瓦照射30分鐘，完成後，在GC注射口以300℃脫附5分鐘進行GC-ECD分析。偵測線性範圍為10-800ng/L，偵測極限為2ng/L，相關係數在0.99以上。
為驗證本方法的可行性，應用此技術於真實樣品中，成功的偵測於工廠廢水中、疏水性紡織布及ABS、PMMA樹脂中含有BDE-209。工廠廢水回收率試驗，可得回收率為77%~95%之間。利用微波輔助頂空固相微萃取技術結合氣相層析法偵測多溴二苯醚，具有快速、操作簡便、不受基質干擾及無需使用有機溶劑等優點，且方法具有良好的靈敏度，並可以很順利的偵測樣品中多溴二苯醚。微波輔助萃取針對高沸點分析物可以有效縮短萃取的時間，並且結合頂空固相微萃取可以降低樣品中基質干擾，有效的降低偵測極限。

A modified headspace solid-phase micro-extraction (HS-SPME) method was studied for the extraction of polybrominated diphenyl ethers (PBDEs) from aqueous samples, before gas chromatographic (GC) analysis with electron capture detection (ECD). Microwave heating was applied to accelerate the evaporation of PBDEs into the headspace, and an external-cooling system was used to control the sampling temperature. Conditions influencing extraction efficiency, such as the SPME-fibers, the sampling temperature, microwave power, and irradiation time (the same as sampling time), sample pH, and salt addition were thoroughly optimized. Experimental results indicated that the extraction of PBDEs from a 10-mL aquatic sample was achieved with the best efficiency through the use of 100 μm PDMS fiber, microwave irradiation of 171 W for BDE-28, 47, 99, 100, 153, 154 and 183 (210W for BDE-209), sampling at 10 oC for 30 min. The detections were linear in the concentration of 0.05 – 5 ng/L for BDE-28, 0.1 - 10 ng/L for BDE-47, 99, 100, 153, 154, 5 - 500 ng/L for BDE-183, 10 - 800 ng/L for BDE-209, respectively. Detection limits were found to be 0.01 - 0.03 ng/L (1ng/L for BDE-183 and 2 ng/L for BDE-209). Sample of industrial wastewater was analyzed with recovery between 77 – 95%. Cloth and polymers of ABS and PMMA were also analyzed. The present method was proven to serve as a simple, sensitive, and rapid procedure for PBDEs analysis in an aqueous sample as well as clothes and polymers.

摘要 i
ABSTRACT ii
目錄 iii
圖目錄 v
表目錄 vi
第一章 緒論 1
一、 多溴二苯醚的介紹 1
二、 多溴二苯醚分析樣品前處理技術 4
(一)液相-液相萃取 6
(二)索式萃取技術 6
(三)固相萃取法 7
(四)固相微萃取法 7
三、 微波加熱原理 17
(一)離子傳動 19
(二)偶極轉動 19
(三)微波源功率的輸出與計算 19
(四)微波加熱方式和傳統加熱方式的比較 21
(五)微波在化學反應中的功能 21
四、 研究目的 21
第二章 試驗材料及研究方法 26
一、藥品、器材及儀器設備 26
(一)藥品 26
(二)器材及儀器設備 27
二、 藥品配置 28
三、 玻璃器皿的矽烷化 31
四、 氣相層析儀條件之設定 32
五、 固相微萃取纖維之活化 32
六、 微波輔助頂空固相微萃取裝置之建立 32
七、 實驗步驟及最佳化條件探討 35
(一)微波輔助頂空固相微萃取實驗步驟 35
(二)固相微萃取纖維種類探討 35
(三)最佳微波照射條件探討 35
(四)樣品pH值探討 36
(五)鹽類添加探討 37
(六)固相微萃取纖維熱脫附條件探討 37
(七)水溶液中多溴二苯醚之校正曲線範圍、校正曲線方程式、校正曲線相關係數及偵測極限值的探討 38
(八)方法精密度探討 39
(九)真實樣品測定 40
(十)真實樣品回收率探討 40
(十一)它種樣品之應用 40
第三章 結果與討論 41
一、氣相層析儀條件與分離管柱之選擇 41
二、 微波輔助頂空固相微萃取最佳化條件探討 51
(一)固相微萃取纖維種類選擇 51
(二)最佳微波照射條件探討 54
1.微波功率的探討 54
2. 微波照射時間的探討 57
3. 冷凝系統溫度的影響 60
(三)樣品pH值探討 63
(四)鹽類添加探討 63
(五)固相微萃取纖維熱脫附條件探討 68
1. 熱脫附溫度探討 68
2. 熱脫附時間探討 71
三、方法可行性之評估 74
(一)校正曲線及偵測極限 74
(二)精密度探討 78
四、真實樣品之分析 80
(一)直接檢測 80
(二)以添加方式檢測 80
五、他種樣品應用 80
六、與現有方法比較 80
第四章 結論 87
第五章 參考文獻 88

1.De Wit, C. A., An overview of brominated flame retardants in the environment. Chemosphere 2002, 46, (5), 583-624.
2.Crump, D.; Jagla, M. M.; Chiu, S.; Kennedy, S. W., Detection of PBDE effects on mRNA expression in chicken (Gallus domesticus) neuronal cells using real-time RT-PCR and a new differential display method. Toxicology in Vitro 2008, 22, (5), 1337-1343.
3.Wang, Y. F.; Wang, S. L.; Chen, F. A.; Chao, H. A.; Tsou, T. C.; Shy, C. G.; Pepke, O.; Kuo, Y. M.; Chao, H. R., Associations of polybrominated diphenyl ethers (PBDEs) in breast milk and dietary habits and demographic factors in Taiwan. Food and Chemical Toxicology 2008, 46, (6), 1925-1932.
4.Polo, M.; Gomez-Noya, G.; Quintana, J. B.; Llompart, M.; Garcia-Jares, C.; Cela, R., Development of a Solid-Phase Microextraction Gas Chromatography/Tandem Mass Spectrometry Method for Polybrominated Diphenyl Ethers and Polybrominated Biphenyls in Water Samples. Analytical Chemistry. 2004, 76, (4), 1054-1062.
5.Andersson, O.; Blomkvist, G., Polybrominated aromatic pollutants found in fish in Sweden. Chemosphere 1981, 10, (9), 1051-1060.
6.Zhou, J.; Yang, F.; Cha, D.; Zeng, Z.; Xu, Y., Headspace solid-phase microextraction with novel sol-gel permethylated-[beta]-cyclodextrin/hydroxyl-termination silicone oil fiber for determination of polybrominated diphenyl ethers by gas chromatography-mass spectrometry in soil. Talanta 2007, 73, (5), 870-877.
7.Yus, V.; Pastor, A.; de la Guardia, M., Microwave-assisted extraction of polybrominated diphenyl ethers and polychlorinated naphthalenes concentrated on semipermeable membrane devices. Analytica Chimica Acta 2006, 565, (1), 103-111.
8.Hyotylainen, T.; Hartonen, K., Determination of brominated flame retardants in environmental samples. TrAC Trends in Analytical Chemistry 2002, 21, (1), 13-30.
9.Ohta, S.; Ishizuka, D.; Nishimura, H.; Nakao, T.; Aozasa, O.; Shimidzu, Y.; Ochiai, F.; Kida, T.; Nishi, M.; Miyata, H., Comparison of polybrominated diphenyl ethers in fish, vegetables, and meats and levels in human milk of nursing women in Japan. Chemosphere 2002, 46, (5), 689-696.
10.Bi, X.; Qu, W.; Sheng, G.; Zhang, W.; Mai, B.; Chen, D.; Yu, L.; Fu, J., Polybrominated diphenyl ethers in South China maternal and fetal blood and breast milk. Environmental Pollution 2006, 144, (3), 1024-1030.
11.Roosens, L.; Dirtu, A. C.; Goemans, G.; Belpaire, C.; Gheorghe, A.; Neels, H.; Blust, R.; Covaci, A., Brominated flame retardants and polychlorinated biphenyls in fish from the river Scheldt, Belgium. Environment International In Press,Corrected Proof,2008.
12.Palm, A.; Cousins, I. T.; Mackay, D.; Tysklind, M.; Metcalfe, C.; Alaee, M., Assessing the environmental fate of chemicals of emerging concern: a case study of the polybrominated diphenyl ethers. Environmental Pollution 2002, 117, (2), 195-213.
13.McDonald, T. A., A perspective on the potential health risks of PBDEs. Chemosphere 2002, 46, (5), 745-755.
14.Hanari, N.; Kannan, K.; Miyake.Y; Okazawa, T.; Kodavanti, P. R. S.; Aldous, K. M.; Yamashita, N., Occurrence of Polybrominated Biphenyls, Polybrominated Dibenzo-p-dioxins, and Polybrominated Dibenzofurans as Impurities in Commercial Polybrominated Diphenyl Ether Mixtures. Environmental Science & Technology. 2006, 40, (14), 4400-4405.
15.Nose, K.; Hashimoto, S.; Takahashi, S.; Noma, Y.; Sakai, S.-i., Degradation pathways of decabromodiphenyl ether during hydrothermal treatment. Chemosphere 2007, 68, (1), 120-125.
16.Ebert, J.; Bahadir, M., Formation of PBDD/F from flame-retarded plastic materials under thermal stress. Environment International 2003, 29, (6), 711-716.
17.Manchester-Neesvig, J. B.; Valters, K.; Sonzogni, W. C., Comparison of Polybrominated Diphenyl Ethers (PBDEs) and Polychlorinated Biphenyls (PCBs) in Lake Michigan Salmonids. Environmental Science & Technology. 2001, 35, (6), 1072-1077.
18.Tseng, L.-H.; Li, M.-H.; Tsai, S.-S.; Lee, C.-W.; Pan, M.-H.; Yao, W.-J.; Hsu, P.-C., Developmental exposure to decabromodiphenyl ether (PBDE 209): Effects on thyroid hormone and hepatic enzyme activity in male mouse offspring. Chemosphere 2008, 70, (4), 640-647.
19.Meerts, I. A. T. M.; van Zanden, J. J.; Luijks, E. A. C.; 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. Society of Toxicology 2000, 56, (1), 95-104.
20.Marsh, A. B., L.G. Bladh, M. Gillner and E. Jakobsson ,, Synthesis of p-hydroxybromodiphenyl ethers and binding to the thyroid receptor. Organohalogen Compounds 37 (1998), pp. 305–308.
21.P. Eriksson, E. J. a. A. F., Developmental neurotoxicity of brominated flame-retardants polybrominated diphenyl ethers and tetrabromo-bis-phenol A. Organohalogen Compounds 35 (1998), pp. 375–377.
22.P. Eriksson, H. V., E. Jakobsson, U. Orn and A. Fredriksson PBDE, 2,2,4,4,5-pentabromodiphenyl ether, causes permanent neurotoxic effects during a defined period of neonatal brain development. Organohalogen Compounds 40 (1999), pp. 33–335.
23.H. Viberg, A. F. a. E. J., Developmental neurotoxic effects of 2,2,4,4,5-pentabromodiphenyl ether (PBDE 99) in the neonatal mouse. Toxicologist 54 (2000), p. 1360
24.H. Viberg, A. F., E. Jakobsson, U. Öhrn and P. Eriksson Brominated flame-retardant: uptake, retention and developmental neuroxic effects of decabromo-diphenyl ether (PBDE 209) in the neonatal mouse. Toxicologist 61 (2001), p. 1034.
25.Covaci, A.; Voorspoels, S.; Roosens, L.; Jacobs, W.; Blust, R.; Neels, H., Polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in human liver and adipose tissue samples from Belgium. Chemosphere In Press, Corrected Proof,2008.
26.Llorca-Porcel, J.; Martinez-Sanchez, G.; Alvarez, B.; Cobollo, M. A.; Valor, I., Analysis of nine polybrominated diphenyl ethers in water samples by means of stir bar sorptive extraction-thermal desorption-gas chromatography-mass spectrometry. Analytica Chimica Acta 2006, 569, (1-2), 113-118.
27.Chao, H.-R.; Wang, S.-L.; Lee, W.-J.; Wang, Y.-F.; Papke, O., Levels of polybrominated diphenyl ethers (PBDEs) in breast milk from central Taiwan and their relation to infant birth outcome and maternal menstruation effects. Environment International 2007, 33, (2), 239-245.
28.Fontanals, N. i.; Barri, T.; Bergstrom, S.; Jonsson, J.-A., Determination of polybrominated diphenyl ethers at trace levels in environmental waters using hollow-fiber microporous membrane liquid-liquid extraction and gas chromatography-mass spectrometry. Journal of Chromatography A 2006, 1133, (1-2), 41-48.
29.Allchin, C. R.; Law, R. J.; Morris, S., Polybrominated diphenylethers in sediments and biota downstream of potential sources in the UK. Environmental Pollution 1999, 105, (2), 197-207.
30.Hagenmaier, H.; She, J.; Benz, T.; Dawidowsky, N.; Dusterhoft, L.; Lindig, C., Analysis of sewage sludge for polyhalogenated dibenzo-p-dioxins, dibenzofurans, and diphenylethers. Chemosphere 1992, 25, (7-10), 1457-1462.
31.Covaci, A.; Voorspoels, S., Optimization of the determination of polybrominated diphenyl ethers in human serum using solid-phase extraction and gas chromatography-electron capture negative ionization mass spectrometry. Journal of Chromatography B 2005, 827, (2), 216-223.
32.Arthur, C. L. P., J, Solid phase microextraction with thermal desorption using fused silica optical fibers. Analytical Chemistry 1990, 62, (19), 2145-8.
33.Pawliszyn, J. b., Solid Phase Microextraction: Theory and Practice. 1997; p 275 pp.
34.Zhang, Z. Y., M. J.; Pawliszyn, J, Solid-Phase Microextraction. A Solvent-Free Alternative for Sample Preparation. Analytical Chemistry 1994, 66, (17), 844A-854A.
35.Zhan, J. L., Sheming; Meng, Zhaoyu; Xiang, Nengjun; Cao, Qiu''e; Miao, Mingming, nalysis of volatile components in Qingshanlvshui tea using solid-phase microextraction/accelerated solvent extraction-gas chromatography-mass spectrometry. Sepu (2008), 26(3), 301-305.
36.Yan, L. Z., Yanfang; Tao, Wenyi; Wang, Liping; Wu, Shengfang, Rapid determination of volatile flavor compounds in soy sauce using head space solid-phase microextraction and gas chromatography-mass spectrometry. Sepu 2008), 26(3), 285-291.
37.Park, G.-B. L., Sueg-Geun, Determination of volatile organic compounds (VOCs) in drinking water using solid phase microextraction (SPME). Analytical Science & Technology (2000), 13(3), 277-281.
38.Ho, W.-H. H., S.-J, Solid phase microextraction associated with microwave assisted extraction of organochlorine pesticides in medicinal plants. Analytica Chimica Acta (2001), 428(1), 111-120.
39.Aresta, A. C., C. D.; Palmisano, F.; Zambonin, C. G, Determination of clenbuterol in human urine and serum by solid-phase microextraction coupled to liquid chromatography. Journal of Pharmaceutical and Biomedical Analysis (2008), 47(3), 641-645.
40.Sporkert, F. P., Fritz, Determination of lidocaine in hair of drug fatalities by headspace solid-phase microextraction. ournal of Analytical Toxicology (2000), 24(5), 316-322.
41.Supelco, Instructions for the Supelco Solid Phase MicroExtraction Fiber Holder for Manual Use, .
42.魏銘琪, 開發微波輔助頂空固相微萃取技術結合氣象層析法分析半揮發性有機污染物之研究 2003博士論文.
43.Lord, H. P., J., Evolution of solid-phase microextraction technology. Journal of Chromatography A 2000, 885, (1-2), 153-193.
44.Gorecki, T. Y., X.; Pawliszyn, J., Theory of analyte extraction by selected porous polymer SPME fibers. Analyst (Cambridge, United Kingdom) 1999, 124, (5), 643-649.
45.Kingston, H. M. J., L. B., Introduction to microwave sample preparation : theory and practice. .
46.Microwave assisted acid leach of aqueous samples and extracts. In EPA Method
47.Dodder, N. G.; Strandberg, B.; Hites, R. A., Concentrations and Spatial Variations of Polybrominated Diphenyl Ethers and Several Organochlorine Compounds in Fishes from the Northeastern United States. Environmental Science & Technology. 2002, 36, (2), 146-151.
48.de Boer, J.; Cofino, W. P., First world-wide interlaboratory study on polybrominated diphenylethers (PBDEs). Chemosphere 2002, 46, (5), 625-633.
49.Ramos, J. J.; Gomara, B.; Fernandez, M. A.; Gonzalez, M. J., A simple and fast method for the simultaneous determination of polychlorinated biphenyls and polybrominated diphenyl ethers in small volumes of human serum. Journal of Chromatography A 2007, 1152, (1-2), 124-129.
50.Eljarrat, E.; Labandeira, A.; Marsh, G.; Rald, D.; Barcel, D., Decabrominated diphenyl ether in river fish and sediment samples collected downstream an industrial park. Chemosphere 2007, 69, (8), 1278-1286.
51.Sanchez-Brunete, C.; Miguel, E.; Tadeo, J. L., Determination of polybrominated diphenyl ethers in soil by ultrasonic assisted extraction and gas chromatography mass spectrometry. Talanta 2006, 70, (5), 1051-1056.
52.Salgado-Petinal, C. G.-C., Maria; Llompart, Maria; Garcia-Jares, Carmen; Cela, Rafael., Headspace solid-phase microextraction gas chromatography tandem mass spectrometry for the determination of brominated flame retardants in environmental solid samples. Analytical and Bioanalytical Chemistry (2006), 385(3), 637-644.
53.Cathrine Thomsen, E. L. G. B., A simplified method for determination of tetrabromobisphenol A and polybrominated diphenyl ethers in human plasma and serum. Journal of Separation Science 2001, 24, (4), 282-290.
54.Christensen, J. H.; Glasius, M.; Pecseli, M.; Platz, J.; Pritzl, G., Polybrominated diphenyl ethers (PBDEs) in marine fish and blue mussels from southern Greenland. Chemosphere 2002, 47, (6), 631-638.
55.Anne P. Vonderheide, M. M.-B. a. J. A. C., Development and application of a method for the analysis of brominated flame retardants by fast gas chromatography with inductively coupled plasma mass spectrometric detection.J. Anal. At. Spectrom 2002, 17, 1480 - 1485.
56.Kazda, R.; Hajslov, J.; Poustka, J.; Cajka, T., Determination of polybrominated diphenyl ethers in human milk samples in the Czech Republic: Comparative study of negative chemical ionisation mass spectrometry and time-of-flight high-resolution mass spectrometry. Analytica Chimica Acta 2004, 520, (1-2), 237-243.
57.Kierkegaard, A.; Bignert, A.; Sellstrom, U.; Olsson, M.; Asplund, L.; Jansson, B.; de Wit, C. A., Polybrominated diphenyl ethers (PBDEs) and their methoxylated derivatives in pike from Swedish waters with emphasis on temporal trends, 1967-2000. Environmental Pollution 2004, 130, (2), 187-198.
58.Xiao, Q.; Hu, B.; Duan, J.; He, M.; Zu, W., Analysis of PBDEs in Soil, Dust, Spiked Lake Water, and Human Serum Samples by Hollow Fiber-Liquid Phase Microextraction Combined with GC-ICP-MS. Journal of the American Society for Mass Spectrometry 2007, 18, (10), 1740-1748.
59.鍾仁棋; 潘復華 矽烷化物在環境分析化學上之應用; 環保署環境檢驗所.
60.張孟淳, 微波輔助衍生化同步頂空固相微萃取技術結合氣相層析法偵測水中全氟羧酸 2007碩士論文.
61.Wang, J.-X.; Jiang, D.-Q.; Gu, Z.-Y.; Yan, X.-P., Multiwalled carbon nanotubes coated fibers for solid-phase microextraction of polybrominated diphenyl ethers in water and milk samples before gas chromatography with electron-capture detection. Journal of Chromatography A 2006, 1137, (1), 8-14.