以超音波輔助分散式液液微萃取法搭配氣相層析電子捕捉負離子質譜儀檢測水樣中的氯化耐燃劑

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：18

、訪客IP：13.59.166.87

姓名

謝懷廣(Huai-kuang Hsieh) 查詢紙本館藏

畢業系所

化學學系

論文名稱

以超音波輔助分散式液液微萃取法搭配氣相層析電子捕捉負離子質譜儀檢測水樣中的氯化耐燃劑

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]

本電子論文使用權限為同意立即開放。
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。
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)

Mirex是個高度氯化的耐燃劑，在1960年代中期開始被拿來當作農藥，然後也被添加於塑膠、橡膠、塗料、電器產品中做為耐燃劑。因為毒性的關係使得這種化學物質在1970年代被禁止，而由其它像是Dechlorane 602 (簡稱Dec 602)、Dechlorane 603 (簡稱Dec 603)、Dechlorane 604 (簡稱Dec 604)這些高度氯化的化合物所取代，特別是耐燃特性與Mirex相似的Dechlorane Plus (簡稱DP)。
以超音波輔助分散式液液微萃取法(UA-DLLME)搭配氣相層析-電子捕捉負離子質譜儀(GC-ECNI-MS)開發出一個簡單，且有機溶劑用量少的方法，以檢測水樣中的五個氯化耐燃劑為本研究的主要目標。將影響來自水樣中待測物萃取效率的參數進行了有系統的研究。最佳化條件為將1 mL乙腈(作為分散劑)以及60 μL四氯化碳(做為萃取劑)的混合液快速注入於10 mL含有0.5克氯化鈉的水樣中。經過1分鐘的超音波震盪後，以6000 rpm的速率(大約3940 g)離心10分鐘。取出沉澱相並且吹乾，接著以50 μL的內標準品回溶就可以進行之後的GC-ECNI-MS分析。偵測極限為0.05-0.5 ng/L。對其做精密度及準確度的測試，其相對標準偏差(RSDs)皆小於10 %，在不同的水樣中測得的總濃度範圍是從0.15至0.33 ng/L。
整體來說，超音波輔助分散式液液微萃取是一個很好的替代萃取方法，用來測定環境水樣中的氯化耐燃劑，因為它是一個簡單、花費低、快速、且對環境友善的分析方法。

摘要(英)

Mirex was a highly chlorinated flame retardant. During the mid-1960s, it was used as a pesticide and also as a flame retardant in plastics, rubber, paint, and electrical goods. The nonagricultural uses of this chemical were banned in the 1970s because of its toxicity, and then partially replaced by other highly chlorinated compounds, such as Dechlorane 602, Dechlorane 603, Dechlorane 604 and, in particular, Dechlorane Plus, which have flame-retardant properties similar to that of mirex.
A simple and solvent-minimized procedure for the determination of five chlorinated flame retardant in aqueous samples using ultrasound-assisted dispersive liquid-iquid microextraction (UA-DLLME) coupled with gas chromatography–electron-capture negative ion mass spectrometry (GC-ECNI-MS) is presented. The parameters affecting the extraction efficiency of analytes from water samples were systematically investigated. The best extraction conditions involved the rapid injection of a mixture of 1.0 mL of acetonitrile (as a dispersant) and 60 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 for 10 min at 6,000 rpm(ca. 3940 g). The sedimented phase was evaporated to dryness and re-dissolved in 50 μL of acetone containing internal standard for further GC-ECNI-MS analysis. The limits of detection were 0.05-0.5 ng/L. The precision for these analytes, as indicated by relative standard deviations (RSDs), was less than 10% for both intra- and inter-day analysis. Their total concentrations were determined in the range from 0.15 to 0.33 ng/L in various water samples.
Overall, UA-DLLME appears to be a good alternative extraction method for the determination of chlorinated flame retardants in environmental water samples, in that it is a simple, low cost, rapid, and eco-friendly analytical method.

關鍵字(中)

★ 氯化耐燃劑
★ 超音波輔助分散式液液微萃取
★ 氣相層析電子捕捉負離子質譜儀

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 耐燃劑 5
2-1-1 耐燃劑簡介 5
2-1-2 耐燃劑之分類 7
2-1-3 Dechloranes簡介 8
2-2 Dechloranes 9
2-2-1 Dechlorane Plus簡介 9
2-2-2 Dechlorane 602、603、604簡介 11
2-2-3 Dechloranes性質 12
2-2-4 Dechloranes之毒性 14
2-3 國外相關研究 17
2-4氣相層析質譜儀 25
2-4-1 四極矩質譜儀 27
2-4-2 化學游離法 28
2-4-3 選擇離子偵測法 31
2-5分散式液液微萃取法 32
2-5-1 前言 32
2-5-2 分散式液液微萃取法原理 33
2-5-3 分散式液液微萃取法流程 34
2-5-4 影響分散式液液微萃取法常見之因素 35
2-5-5 分散式液液微萃取法的應用 37
2-5-6 分散式液液微萃取法的發展 37
2-6超音波輔助乳化微萃取 42
2-7超音波輔助分散式液液微萃取 44
2-8 線性迴歸 45
2-8-1 Mandel Test 45
2-8-2 缺適性檢定(Lack-of -Fit Test) 48
2-9 基質效應 50
第三章實驗步驟與樣品分析 53
3-1 實驗藥品與儀器設備 53
3-1-1 實驗藥品 53
3-1-2 儀器設備 56
3-2 實驗步驟 57
3-2-1 標準品的製備 57
3-2-2 氣相層析質譜儀參數設定 58
3-2-3 超音波輔助分散式液液微萃取步驟 61
3-3 水樣採集 62
第四章結果與討論 63
4-1氯化耐燃劑的測定 63
4-1-1 氣相層析質譜儀對氯化耐燃劑的檢測 63
4-1-2 檢量線及偵測極限 68
4-2 超音波輔助分散式液液微萃取條件最佳化 70
4-2-1 萃取劑的種類 70
4-2-2 分散劑的種類 73
4-2-3 萃取劑的體積 74
4-2-4 分散劑的體積 75
4-2-5 超音波震盪時間 76
4-2-6 鹽類的添加量 78
4-2-7 超音波輔助分散式液液微萃取的最佳化結果 79
4-3 線性方程式適用性 80
4-4 基質效應 82
4-5 真實樣品之檢測 84
4-6 方法精密度及準確度 91
4-7 方法比較 92
第五章結論與建議 93
5-1 結論 93
5-2 建議 94
第六章參考文獻 95
附錄 106

參考文獻

 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，民國九十五年。
 Barón, E.; Eljarrat, E.; Barceló, D., Analytical method for the determination of halogenated norbornene flame retardants in environmental and biota matrices by gas chromatography coupled to tandem mass spectrometry. J. Chromatogr. A, 2012, 1248, 154–160.
 Berijani, S.; Assadi, Y.; Anbia, M.; Hosseini, M. R. M.; Aghaee, E., Dispersive liquid–liquid microextraction combined with gas chromatography-flame photometric detection. Very simple, rapid and sensitive method for the determination of organophosphorus pesticides in water. J. Chromatogr. A, 2006, 1123, 1–9.
 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.
 Chen, H.; Chen, R.; Li, S., Low-density extraction solvent-based solvent terminated dispersive liquid–liquid microextraction combined with gas chromatography–tandem mass spectrometry for the determination of carbamate pesticides in water samples. J. Chromatogr. A, 2010, 1217, 1244–1248.
 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.
 Du, J.; Yan, H.; She, D.; Liu, B.; Yang, G., Simultaneous determination of cypermethrin and permethrin in pear juice by ultrasound-assisted dispersive liquid-liquid microextraction combined with gas chromatography. Talanta, 2010, 82, 698–703.
 Fan, Y. C.; Hu, Z. L.; Chen, M. L.; Tu, C. S.; Zhu, Y., Ionic liquid based dispersive liquid–liquid microextraction of aromatic amines in water samples. Chin. Chem. Lett., 2008, 19, 985–987.
 Farajzadeh, M. A.; Mogaddam, M. R. A., Air-assisted liquid–liquid microextraction method as a novel microextraction technique; Application in extraction and preconcentration of phthalate esters in aqueous sample followed by gas chromatography–flame ionization detection. Anal. Chim. Acta, 2012, 728, 31–38.
 Fatemi, M. H.; Hadjmohammadi, M. R.; Shakeri, P.; Biparva, P., Extraction optimization of polycyclic aromatic hydrocarbons by alcoholic-assisted dispersive liquid–liquid microextraction and their determination by HPLC. J. Sep. Sci., 2012, 35, 86–92.
 Feo, M. L.; Barón, E.; Eljarrat, E.; Barceló, D., Dechlorane Plus and related compounds in aquatic and terrestrial biota : a review. Anal Bioanal Chem , 2012, 404, 2625–2637.
 Guerra, P.; Fernie, K.; Jiménez, 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 indication of Dechlorane compounds in marine environment of northern China. Environ. Sci. Technol., 2011, 45, 2613–2618.
 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.
 Leong, M. I.; Chang, C. C.; Fuh, M. R.; Huang, S. D., Low toxic dispersive liquid-liquid microextraction using halosolvents for extraction of polycyclic aromatic hydrocarbons in water samples. J. Chromatogr. A, 2010, 1217, 5455–5461.
 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, 1211, 8–12.
 Ma, W. L.; Liu, L. Y.; Qi, H.; Sun, D. Z.; Shen, J. M.; Wang, D. G.; Li, Y. F., Dechlorane Plus in multimedia in northeastern Chinese urban region. Environ. Int., 2011, 37, 66–70.
 MÖller, A.; Xie, Z.; Caba, A.; Sturm, R.; Ebinghaus, R., Occurrence and air-seawater exchange of brominated flame retardants and Dechlorane Plus in the North Sea. Atmos. Environ., 2012, 46, 346–353.
 MÖller, A.; Xie, Z.; Cai, M.; Zhong G.; Huang, P.; Cai, M.; Sturm, R.; He, J.; Ebinghaus, R., Polybrominated diphenyl ethers vs Alternate Brominated flame retardants and Dechloranes from East Asia to the Arctic. Environ. Sci. Technol., 2011, 45, 6793–6799.
 MÖller, A.; Xie, Z.; Sturm, R.; Ebinghaus, 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.; Roscales, J. L.; Vicente, A.; Aguirre, J. I.; Jiménez, B., Dechlorane Plus in eggs of two gull species (Larus michahellis and Larus audouinii) from the southwestern Mediterranean Sea. Anal Bioanal Chem , 2012, 404, 2765–2773.
 Muñoz-Arnanz, J.; Sáez, M.; Hiraldo, F.; Baos, R.; Pacepavicius, G.; Alaee, M.; Jiménez, B., Dechlorane plus and possible degradation products in white stork eggs from Spain. Environ. Int., 2011, 37, 1164–1168.
 OxyChem. Dechlorane Plus ○R (all grades). Safety data sheet. MSDS No.: M41759. 2011. Available at http://msds.oxy.com/DWFiles/M41759_ROW_BE%234.pdf
 Qi, H.; Liu, L.; Jia, H.; Li, Y. F.; Ren, N. Q.; You, H.; Shi, X.; Fan, L.; Ding, Y., Dechlorane Plus in surficial water and sediment in a northeastern Chinese river. Environ. Sci. Technol., 2010, 44, 2305–2308.
 Qiu, X.; Hites, R. A., Dechlorane Plus and other flame retardants in tree bark from the northeastern United States. Environ. Sci. Technol., 2008, 42, 31–36.
 Qiu, X.; Marvin, C. H.; Hites, R. A., Dechlorane Plus and other flame retardants in a sediment core from Lake Ontario. Environ. Sci. Technol., 2007, 41, 6014–6019.
 Qiu, X.; Zhu, T.; Hu, J., Polybrominated diphenyl ethers (PBDEs) and other flame retardants in the atmosphere and water from Taihu Lake, East China. Chemosphere, 2010, 80, 1207–1212.
 Regueiro, J.; Llompart, M.; Garcia-Jares, C.; Garcia-Monteagudo, J. C.; Cela, R., Ultrasound-assisted emulsification-microextraction of emergent contaminants and pesticides in environmental waters. J. Chromatogr. A, 2008, 1190, 27–38.
 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.
 Ren, N.;Sverko, E.; Li, Y. F.; Zhang, Z.; Harner, T.; Wang, D.;Wan, X.; McCarry, B. E., Levels of isomer profiles of Dechlorane Plus in Chinese air. Environ. Sci. Technol., 2008, 42, 6476–6480.
 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.
 Richardson, S. D., Environmental Mass Spectrometry: Emerging Contaminants and Current Issues. Anal. Chem, 2006, 78 , 4021-4045.
 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.
 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.
 Skoog, D. A.; Holler, F. J.; Crouch, S. R., Principles of instrumental analysis. 6th ed., Thomson-Brooks/Cole, 2007.
 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. 2009. Available at http://www.epa.gov/chemrtk/pubs/summaries/dechlorp/c15635rr3.pdf.
 Wang, D. G.; Alaee, M.; Byer, J. D.; Brimble, S.; Pacepavicius, G., Human health risk assessment of occupational and residential exposures to dechlorane plus in the manufacturing facility area in China and comparison with e-waste recycling site. Sci. Total Environ., 2013, 445-446, 329–336.
 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.; Lou, 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.
 Wu, Q.; Chang, Q.; Wu, C.; Rao, H.; Zeng, X.; Wang, C.; Wang, Z., Ultrasound-assisted surfactant-enhanced emulsification microextraction for the determination of carbamate pesticides in water samples by high performance liquid chromatography. J. Chromatogr. A, 2010, 1217, 1773–1778.
 Xian, Q.; Siddique, S.; Li, T.; Feng, Y. L.; Takser, L.; Zhu, J., Sources and environmental behavior of dechlorane plus — A review. Environ. Int., 2011, 37,1273–1284.
 Yan, H.; Liu, B.; Du, J.; Row, K. H., Simultaneous determination of four phthalate esters in bottled water using ultrasound-assisted dispersive liquid–liquid microextraction followed by GC-FID detection. Analyst, 2010, 135, 2585–2590.
 Yiantzi, E.; Psillakis, E.; Tyrovola, K.; Kalogerakis, N., Vortex-assisted liquid–liquid microextraction of octylphenol, nonylphenol and bisphenol-A. Talanta, 2010, 80, 2057–2062.
 Zgoła-Grzes´kowiak, A.; Grzes´kowiak, T., Dispersive liquid–liquid microextraction. Trends Anal. Chem., 2011, 30, 1382–1999.
 Zhang, Y.; Lee, H. K., Determination of ultraviolet filters in water samples by vortex-assisted dispersive liquid–liquid microextraction followed by gas chromatography–mass spectrometry. J. Chromatogr. A, 2012, 1249, 25–31.
 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.
 Zhou, N.; Liu, L.; Qi, H.; Ma, W.; Li, Y. F., Isomer of Dechlorane Plus in surfacial water, soil and sediment in a Northern Chinese wetlands. Organohalogen Compd., 2011, 73, 2232–2235.
 Zhou, S. N.; Reiner, E. J.; Marvin, C. H.; Helm, P.A.; Shen, L.; Brindle, I. D., Liquid chromatography/atmospheric pressure photoionization tandem mass spectrometry for analysis of Dechloranes. Rapid Commun.Mass Spectro., 2011, 25, 436–442.
 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

審核日期

2013-7-9

推文