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研究生： 謝懷廣
Huai-kuang Hsieh
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
指導教授： 丁望賢
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
論文出版年： 2013
畢業學年度： 101
語文別： 中文
論文頁數： 126
中文關鍵詞： 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
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    • 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。

    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.

    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

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