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研究生: 楊清雅
Ching-ya Yang
論文名稱: 以超音波輔助分散式液液微萃取法萃取水樣中的多環麝香化合物之方法開發
Ultrasound-assisted dispersive liquid-liquid microextraction for the rapid determination of synthetic polycyclic musks in aqueous samples
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: 99
語文別: 中文
論文頁數: 116
中文關鍵詞: 合成麝香超音波輔助分散式液液微萃取
外文關鍵詞: Ultrasound-assisted dispersive liquid-liquid mic, synthetic polycyclic musks
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  •   近年來一群合成麝香香料於市面上廣泛的被使用,其中多環類麝香化合物在環境大氣、淡水、海洋及底泥中已陸續被檢出,此外這類化合物由於親脂性強,因而容易聚集在水中生物的體內,及肌肉細胞中,甚至在人體的脂肪組織及母乳中均檢測出有這類化合物的存在。這類化合物已被證實具有雌激素活性存在,易導致雌化現象產生,此外這類化合物隨著女性血液中所測得的濃度增加而增加女性導致小產的機率。
      本研究將使用目前新開發的一項簡單,且以少量有機溶劑,即可同時搭配氣相層析質譜儀鑑定六種多環類麝香化合物的前處理方法,此方法為,超音波輔助分散式液液微萃取法(Ultrasound-assisted Dispersive Liquid-Liquid Microextraction,簡稱UA-DLLME),研究中將探討幾個影響萃取的因素(如分散劑及有機萃取溶劑的選擇、添加鹽類的量等)並做最佳化。萃取的最佳條件為以比例1000 μL / 10 μL 的IPA(分散劑)/CCl4(萃取劑)做為萃取溶劑,將其打入10 mL水樣(含0.5 g NaCl)的尖底玻璃離心管中,接著經由超音波震盪1分鐘後,以5000 rpm離心10分鐘,抽取底部1 μL的液滴進入GC-MS中進樣。
    此方法的定量極限(Limit of Quantification,簡稱LOQ)則低於0.5 ng/L。精密度所產生的相對標準偏差範圍均小於13%,回收率所表示的準確度可達到62-104%之間。在環境水樣中,搭配標準添加法,所得定量結果介於8.3至63.9 ng/L之間。
      本研究所發展的方法,提供了迅速、簡便、節省、環境汙染小及靈敏度與再現佳等優點。是一項可廣泛應用的前處理方式。


      Currently, a group of widely used synthetic musk fragrances, synthetic polycyclic musks have been detected in air, freshwater, seawater and sediment samples. Because of their highly lipophilic properties, polycyclic musks have been also found in aquatic biota, such as mussels and fish, and even in human adipose tissue and breast milk. These compounds have demonstrated estrogenic activity, even higher concentrations of synthetic polycyclic musks in women''s bloods have been correlated to higher rate of miscarriage.
      In this study, a simple and solvent-less procedure was developed for the determination of six commonly found synthetic polycyclic musks in aqueous samples using ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) coupled gas chromatography-mass spectrometry (GC-MS). The parameters affecting the extraction efficiency of analytes from water samples were systematically investigated and the conditions optimized. The best extraction conditions involved the rapid injection of a mixture of 1.0 mL of isopropyl alcohol (as a dispersant) and 10 μL of carbon tetrachloride (as an extractant) into 10 mL of water containing 0.5 g of sodium chloride in a conical bottom glass tube. After ultrasonication for 1.0 min and centrifugation at 5000 rpm (10 min), the sedimented phase 1.0 μL was directly injected into the GC-MS system. The limits of quantitation (LOQs) were less than 0.5 ng/L. The precision for these analytes, as indicated by relative standard deviations (RSDs), were less than 13% for both intra- and inter-day analysis. Accuracy, expressed as the mean extraction recovery, was between 62 and 104%. Using a standard addition method, their total concentrations were determined to be in the range from 8.3 to 63.9 ng/L in various environmental samples.
      The developed technique appears to be a good alternative extraction method for the determination of organic compounds in environmental water samples in that it is a simple, low cost, effective, and eco-friendly analytical method.

    中文摘要 I Abstract 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 3 2-1  藥物與個人護理產品 4 2-1-1 藥物與個人護理產品的來源 5 2-1-2 合成麝香 6 2-1-3 多環麝香 11 2-1-4 多環類麝香化合物於生物體中的汙染狀況 13 2-1-5 多環麝香化合物的毒性探討 20 2-1-6 相關研究文獻 25 2-2  超音波輔助萃取法(Ultrasound-assisted extraction) 34 2-3  分散式液液微萃取 35 2-3-1 引言 35 2-3-2 原理 36 2-3-3 分散式液液微萃萃取效率的影響因素 38 2-3-4 分散式液液微萃的應用 39 2-3-5 總結 42 2-4  氣相層析質譜儀 48 2-4-1 質譜儀(Mass Spectrometry) 49 2-4-2 電子游離法(Electron ionization) 50 2-4-3 四極矩質譜儀(Quadrupole mass analyzer) 51 第三章 實驗步驟與樣品分析 53 3-1  實驗藥品與設備 53 3-1-1 實驗藥品 53 3-1-2 儀器設備 54 3-2  實驗步驟 56 3-2-1 標準品的配製 56 3-2-2 氣相層析質譜儀的參數設定 57 3-2-3 操作流程 59 3-2-4 實驗條件探討 60 3-3  水樣採集 61 第四章 結果與討論 62 4-1  氣相層析質譜儀對多環類麝香化合物的測定 62 4-1-1 多環類麝香化合物的分析 62 4-1-2 儀器的偵測極限 67 4-2  超音波輔助分散式液液微萃取萃取 69 4-2-1 計算萃取濃縮倍率及萃取回收率 70 4-2-2 萃取劑的選擇 71 4-2-3 分散劑的選擇 75 4-2-4 萃取劑體積量的選擇 78 4-2-5 分散劑量的選擇 80 4-2-6 超音波震盪時間選擇 82 4-2-7 鹽的添加對萃取的影響 85 4-2-8 pH的影響 87 第五章 結論 103 第六章 參考文獻 105

    ? 台北野生物貿易研究委員會、TRAFFIC EAST ASIA-TAIPEI、
    行政院農業委員會林務局 共同製作:常見華盛頓公約植物指南,2008年12月
    ? 梁美怡、黃賢達,冷凝分散液液萃取法,民國97年7月
    ? 周作穎、傅明仁,分散式液液微萃取技術搭配液相層析聯結光二
    偶極陣列偵測器檢測環境水中之苯脲型除草劑,民國98年6月
    ? 空穴現象產生圖:http://www.lockstockuae.com/storz_shockwave
    ? Balk, F. ; Blok, H. ; Salvito, D. , ”Environmental Risks of Musk Fragrance Ingredients” American Chemical Society, 2001
    ? Berset, J. D. ; Kupper, T. ; Etter, R. ; Tarradellas, J. , ” Considerations about the enantioselective transformation of polycyclic musks in wastewater, treated wastewater and sewage sludge and analysis of their fate in a sequencing batch reactor plant” Chemosphere, 2004, 57, 987–996
    ? Chen, D. ; Zeng, X. ; Sheng, Y. ; Bi, X. ; Gui, H. ; Sheng, G. ; Fu, J. , ”The concentrations and distribution of polycyclic musks in a typical cosmetic plant” Chemosphere, 2007, 66, 252–258
    ? Chen, X. ; Bester, K. ; “Determination of organic micro-pollutants such as personal care products, plasticizers and flame retardants in sludge” Anal Bioanal Chem, 2009, 395, 1877–1884
    ? Chiang, J. S. ; Huang, S. D. , “Simultaneous derivatization and extraction of anilines in waste water with dispersive liquid–liquid microextraction followed by gas chromatography–mass spectrometric detection” Talanta, 2008, 75 70–75
    ? Dietrich, D. R. ; Chou, Y. J. , “Ecotoxicology of Musks “American Chemical Society, 2001
    ? Dsikowitzky, L. ; Schwarzbauer, J. ; Littke, R. , ”Distribution of polycyclic musks in water and particulate matter of the Lippe River (Germany) “Organic Geochemistry, 2002, 33, 1747–1758
    ? Einsle, T. ; Paschke, H. ; Bruns, K. ; Schrader, S. ; Poppa, P. ; Moedera, M. , “Membrane-assisted liquid–liquid extraction coupled with gaschromatography–mass spectrometry for determination of selected polycyclic musk compounds and drugs in water samples” J. Chromatogr. A, 2006, 1124, 196–204
    ? Eisenhardt, S. ; Runnebaum, B. ; Bauer, K. ; Gerhard, I. , ”Nitromusk compounds in women with gynecological and endocrine dysfunction”. Environ. Res. A, 2001, 87, 123–130
    ? Farajzadeh, M. A. ; Bahram, M. ; Jönsson, J. Å. , “Dispersive liquid–liquid microextraction followed by high-performance
    liquid chromatography-diode array detection as an efficient
    and sensitive technique for determination of antioxidants” Analytica Chimica Acta, 2007, 591, 69–79
    ? Fontana, A. R. ; Wuilloud, R. G. ; Martinez, L. D. ; Altamirano, J. C. , “Simple approach based on ultrasound-assisted emulsification-microextraction for determination of polibrominated flame retardants in water samples by gas chromatography–mass spectrometry” J. Chromatogr. A ,2009, 1216, 147–153
    ? Fu, C. ; Tian, H. ; Li, Q. ; Cai, T. ; Du, W. , “ Ultrasound-assisted extraction of xyloglucan from apple pomace” Sonochemistry , 2006, 13, 511-516
    ? Hu, Z. J. ; Shi, Y. L. ; Cai, Y. Q. , “Determination of synthetic musk fragrances in sewage sludge, sediment and soil using accelerated solvent extraction with gas chromatography-mass spectrometry” Fenxi Huaxue, 2010, 38, 885-888.
    ? Hu, Z. J. ; Shi, Y. L. ; Cai, Y. Q. ,” Determination of polycyclic musks in fish samples by accelerated solvent extraction (ASE) and gas chromatography-mass spectrometry” Huanjing Huaxue, 2011, 30, 362-365
    ? Herrera-Herrera, A.V. ; Asensio-Ramos, M. ; Hernández-Borges, J. ; Rodríguez-Delgado, M. Á. ,” Dispersive liquid-liquid
    microextraction for determination of organic analytes” Trends in Analytical Chemistry, 2010, 29, 7
    ? Hutter, H. P. ; Wallner, P. ; Moshammer, H. ; Hartl, W. ; Sattelberger, R. ; Lorbeer, G. ; Kundi, M. , ”Blood concentrations of polycyclic musks in healthy young adults” Chemosphere, 2005, 59, 487–492
    ? Kannan, K. C. ; Reiner, J. L. ; Yun, S. H. ; Perrotta, E. E. ; Tao, L. ; Johnson-Restrepo, B. ; Rodan, B. D. ,”Polycyclic musk compounds in higher trophic level aquatic organisms and humans from the United States” Chemosphere, 2005, 61, 693–700
    ? Kameda, Y. ; Yamashita, H. ; Ozaki, M. , ” Loads and Removal Rations of Synthetic Fragrance Materials and Organic UV Filters in Sewage Treatment Plants in Japan” Journal of Japan Society on Water Environment, 2008, 31, 367-374
    ? Kevekordes, S. ; Mersch-Sundermann, V. ; Diez, M. ;
    Dunkelberg, H. , “In vitro genotoxicity of polycyclic musk fragrances in the micronucleus test” Mutation Research, 1997, 395, 145–150
    ? Kuklenyik, Z. ; Bryant, X. A. ; Needham, L. L. ; Calafat, A. M. , “SPE/SPME–GC/MS approach for measuring musk compounds in serum and breast milk” J. Chromatogr. B, 2007, 858, 177–183
    ? Lee, H. B . ; Peart, T. E. ; Sarafin, K. , ” Occurrence of Polycyclic and Nitro Musk Compounds in Canadian Sludge and Wastewater Samples” Water Qual. Res. J. Canada, 2003, 38, 683–702
    ? Leong, M. I. ; Huang, S. D. , “Dispersive liquid–liquid microextraction method based on solidification of floating organic drop combined with gas chromatography with electron-capture or mass spectrometry detection “J. Chromatogr. A, 2008, 121, 18–12
    ? Llompart, M. ; García-Jares, C. ; Salgado, C. ; Polo, M. ; Cela, R. , “Determination of musk compounds in sewage treatment plant sludge samples by solid-phase microextraction “J. Chromatogr. A, 2003, 999, 185–193
    ? Loretz, L. J. ; Api, A. M. ; Barraj, L. ; Burdick, J. ; Dressler, W. ; Gettings, S. D. ; Han Hsu, H. ; Pan, Y. H. L. ; Re, T. A. ; Renskers, K. J. ; Rothenstein, A. ; Scrafford, C. G. ; Sewall, C. , “Exposure data for cosmeticproducts: lipstick, body lotion, and face cream” Food Chem. Toxicol., 2005, 43, 279–291.
    ? Loretz, L. J. ; Api, A. M. ; Barraj, L. ; Burdick, J. ; Davis, D. A. ; Dressler, W. ; Gilberti, E. ; Jarrett, G. ; Mann, S. ; Pan, Y. H. L. ; Re, T. ; Renskers, K. ; Scrafford, S. ; Vater, S. , ” Exposure data for personal care products: Hairspray, spray perfume, liquid foundation, shampoo, body wash and solid antiperspirant” Food Chem. Toxicol, 2006, 44, 2008–2018.
    ? Lv, Y. ; Yuan, T. ; Hu, J. Y. ; Wang, W. H. , “Simultaneous Determination of Trace Polycyclic and Nitro Musk in Water Samples
    Using Optimize Solid-Phase Extraction by Gas Chromatography and Mass Spectrometry” Analytical Science September, 2009, 25, 1125-1130
    ? McCarty, L. S. ; Mackay, D. ; Smith, A. D. ; Ozburn, G. W. ; Dixon, D. G. , “ Residue- - based in terpretation of toxicity and bioconcentration QSARs from aquatic bio as says: Neutral narcotic organics,” Environmental Toxicology and Chem is try , 1992, 11, 917- 930.
    ? Moedera, M. ; Schradera, S. ; Winklera, U. ; Rodilb, R. , ”At-line microextraction by packed sorbent-gas chromatography–mass spectrometry for the determination of UV filter and polycyclic musk compounds in water samples” J. Chromatogr. A, 2010, 1217, 2925–2932
    ? Orozco-Solano, M. ; Ruiz-Jimenez, J. ; Luque de Castro, M. D. , “Ultrasound-assisted extraction and derivatization of sterols and fatty alcohols from olive leaves and drupes prior to determination by gas chromatography–tandem mass spectrometry” J. Chromatogr. A, 2010, 1217, 1227–1235
    ? Osemwengie, L. I. ; Gerstenbergerb, S. L. , ” Levels of synthetic musk compounds in municipal wastewater for potential estimation of biota exposure in receiving waters” J. Environ. Moni., 2004, 6, 533 – 539
    ? Panagiotou, A. N. ; Sakkas, V. A. ; Albanis, T. A. , ” Application of chemometric assisted dispersive liquid–liquid microextraction to the determination of personal care products in natural waters” Analytica Chimica Acta, 2009, 649, 135–140
    ? Peck, A. M. ; Hornbuckle, K. , “Synthetic Musk Fragrances in Lake Michigan “Environ. Sci. Technol. , 2004, 38, 367-372
    ? Peck, A. M. , ”Analytical methods for the determination
    of persistent ingredients of personal care products in
    environmental matrices “Anal Bioanal Chem , 2006, 386, 907–939
    ? Pena-Pereira, F. ; Lavilla, I. ; Bendicho, C. , ” Miniaturized preconcentration methods based on liquid–liquid extraction and their
    application in inorganic ultratrace analysis and speciation: A review”
    Spectrochimica Acta Part B, 2009, 64, 1–15
    ? Plassche, E. J. Van de ; Balk, F. , ”Environmental risk assessment of the polycyclic mush AHTN and HHCB according to the EU-TGD” National Institute of Public Health and the Environment: Bilthoven, The Netherlands, 1997
    ? Ramirez, N. ; Marce, R. M. ; Borrull, F. , ” Development of a stir bar sorptive extraction and thermal desorption–gas chromatography–mass spectrometry method for determining synthetic musks in water samples” J. Chromatogr. A,, 2011, 1218, 156–161
    ? Regueiro, J. ; Llompart, M. ; Garcia-Jares, C. ; Garcia-Monteagudob, J. C. ; Cela, R. , “Ultrasound-assisted emulsification–microextraction of emergent contaminants and pesticides in environmental waters” J. Chromatogr. A, 2008, 1190, 27–38
    ? Rezaee, M. ; Assadi, Y. ; Hosseini, M. R. M. ; Aghaee, E. ; Ahmadi, F. ; Berijani, S. , “Determination of organic compounds in water using dispersive liquid–liquid microextraction “J. Chromatogr. A, 2006, 1116, 1–9
    ? Rezaee, M. ; Yamini, Y. ; Faraji, M. ,” Evolution of dispersive liquid–liquid microextraction method” J. Chromatogr. A, 2010, 1217, 2342–2357
    ? Regueiroa, J. ; Llomparta, M. ; Garcia-Jaresa, C. ; Garcia-Monteagudob, J. C. ; Celaa, R. , “Ultrasound-assisted emulsification–microextraction of emergent contaminants and pesticides in environmental waters” J. Chromatogr. A, 2008, 1190, 27–38
    ? Roosens, L. ; Covaci, A. ; Neels, H. , ” Concentrations of synthetic musk compounds in personal care and sanitation products and human exposure profiles through dermal application”Chemosphere , 2007, 69, 1540–1547
    ? Schmid, P. ; Kohler, M. ; Gujer, E. ; Zennegg, M. ; Lanfranchi, M. , ”Persistent organic pollutants, brominated flame
    retardants and synthetic musks in fish from remote alpine lakes in Switzerland”Chemosphere, 2007, 67, S16–S21
    ? Silva, M. ; Nogueira, J. M. , “Stir-bar-sorptive extracton and liquid desorption combined with large volumn injection gas chromatography-mass spectrometry for ultra-trace analysis of musk compunds in environmental water matrices” Anal Bioanal Chem, 2010, 396, 1853-1862
    ? Smyth, S. A. ; Lishman, L. A. ; McBean, E. A. ; Kleywegt, S. ; Yang, J. J. ; Svoboda, M. L. ; Ormonde, S. ;Pileggi, V. ; Lee, H. B. ; Seto, P. , “Polycyclic and Nitro Musks in Canadian Municipal Wastewater : Occurrence and Removal in Wastewater Treatment” Water Qual. Res J. Canada, 2007, 42, 138-152
    ? Svoboda, M. L. ; Yang, J. J. ; Falletta, P. ; Lee, H. B. , “A Microwave-assisted Extraction Method for the Determination of Synthetic Musks in Sewage Sludge “Water Qual.Res Canada , 2007, 42, 11-19
    ? Ternes, T. A. ; Bonerz, M. ; Herrmann, N. ; LÖffler, D. ; Keller, E. ; Lacida, B. B; Alder, A. C. , “Determination of pharmaceuticals, iodinated contrast media and musk fragrances in sludge by LC/tandem MS and GC/MS“J. Chromatogr. A, 2005, 1067, 213–223
    ? Wan, Y. ; Wi, Q. ; Hu, J. ; Jin, X. ; Zang, Z. ; Zen, H. ; Liu, J. , “Levels, Tissue Distribution, and Age-Related Accumulation of Synthetic Musk Fragrances in Chinese Sturgeon (Acipenser sinensis): Comparison to
    Organochlorines“ Environ. Sci. Technol., 2007, 41, 424-430
    ? Wang, Y. C. ; Ding, W. H. ; “ Determination of synthetic polycyclic musks in water by microwave-assisted headspace solid-phase microextraction and gas chromatography-mass
    spectrometry“J. Chromatogr. A, 2009, 1216, 6858–6863
    ? Winklera, M. ; Headleyb, J. V. ; Perub, K. M. , “ Optimization of solid-phase microextraction for the gas
    chromatographic–mass spectrometric determination of synthetic
    musk fragrances in water samples“ J. Chromatogr. A, 2000, 903, 203–210
    ? Wu, S. F. ; Ding, W. H. , “Fast determination of synthetic polycyclic musks in sewage sludge and sediments by microwave-assisted headspace solid-phase microextraction and gas chromatography–mass spectrometry“J. Chromatogr. A, 2010, 1217, 2776–2781
    ? Yamauchia, R. ; Ishibashia, H. ; Hiranoa, M. ; Moria, T. ; Kima, J. W. ; Arizonoa, K. , “Effects of synthetic polycyclic musks on estrogen receptor, vitellogenin,pregnane X receptor, and cytochrome P450 3A gene expression in thelivers of male medaka (Oryzias latipes) “ Aquatic Toxicology , 2008, 90, 261–268
    ? Yang, J. J. ; Metcalfe, C. D. , “Fate of synthetic musks in a domestic wastewater treatment plant and in an agricultural field amended with biosolids“ Science of the Total Environment , 2006, 363, 149– 165
    ? Zeng, X. ; Sheng, G. ; X, Y. ;Fu, J. , “ Determination of polycyclic musks in sewage sludge from Guangdong, China using GC–EI-MS“ Chemosphere ,2005, 60, 817-823
    ? Zhang , X. ; Yao, Y. ; Zeng, X. ; Qian, G. ; Guo, Y. ; Wu, M. ; Sheng, G. ; Fu , J. , “ Synthetic musks in the aquatic environment and personal care products in Shanghai, China “Chemosphere, 2008, 72, 1553–1558

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