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研究生: 劉永豪
論文名稱: 比較垂直震盪器輔助乳化微萃取法與低濃度界面活性劑為分散劑液液微萃取法偵測水樣中雙苯醚類除草劑之效果
The determination of diphenylether herbicides in water samples using HPLC
指導教授: 黃賢達
Huang, Shang-Da
口試委員: 凌永健
黃賢達
陳珮珊
學位類別: 碩士
Master
系所名稱: 理學院 - 化學系
Department of Chemistry
論文出版年: 2013
畢業學年度: 101
語文別: 中文
論文頁數: 78
中文關鍵詞: 垂直震盪器界面活性劑雙苯醚類除草劑微萃取高效能液相層析儀
外文關鍵詞: UDSA-DLLME, WLSEME, diphenylether herbicides, microextraction, HPLC
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  • 除草劑為人類的生活提供一定的便利性,然而隨著雨水沖刷與河川的流動,這些化學物質不經意地就進入環境當中。本篇測定的雙苯醚類除草劑被懷疑具有致癌性,因此能否檢測其含量是個重要議題。
    本研究主要是比較以垂直震盪器輔助乳化與低濃度界面活性劑當分散劑進行液液微萃取法兩者的差異。前者是利用垂直震盪器促使萃取溶劑分散在水中,並搭配快速搖盪增加萃取溶劑與水樣之間的物質交換 (mass transfer);後者則是以界面活性劑使萃取溶劑分散成小液滴後打入樣品內,因為呈現小液滴狀態可增加萃取溶劑與樣品的接觸面積,故可在極短時間內完成萃取。
    經由最佳化過後,垂直震盪器輔助乳化的萃取溶劑是30 μL乙酸癸酯、添加氯化鈉0.25克、震盪時間3分鐘,以5000 rpm轉速離心5分鐘後可在上層獲得萃取液滴,將其取出後以10 μL打入高效能液相層析儀進行分析。此方法的線性濃度在2-1000 μg L-1之間,決定係數 (r2)皆在0.9992以上,偵測極限0.62-1.74 μg L-1之間,低於臺灣放流水標準 (1 mg L-1)。
    界面活性劑為分散劑的方法,最佳化結果是以33 μL的乙酸癸酯為萃取溶劑,濃度1 mg L-1的tween 60為界面活性劑,使用體積150 μL,在不加氯化鈉的情況下進行萃取。此方法的線性濃度在2-1000 μg L-1之間,決定係數 (r2)皆在0.9988以上,偵測極限0.72-1.38 μg L-1之間,亦低於臺灣放流水標準。


    In this study, we compare two methods which are used to detect five diphenylether herbicides. One is up-and-down shaker-assisted emulsion, the other is water with low concentration of surfactant in dispersed solvent-assisted emulsion dispersive liquid–liquid microextraction (WLSEME).
    The first method cause the extraction solvent to form fine droplets in the sample solution by shaking violently. After optimization, this method can finish extraction in three minutes using only 30 μL of decyl acetate. The linear range is 2-1000 μg L-1 and r2 is greater than 0.9992; detection limit is from 0.62 to 1.74 μg L-1. The relative recoveries range from 90 to 102% for river water; 88–104% for lake water and 93–102% for irrigating water.
    The WLSEME method use a microsyringe to withdrew and discharge extraction solvent and 1 mg L-1 tween 60 (as the dispersed solvent) four times within 10 seconds. After that, a cloudy emulsified solution is formed in the syringe. The effect of various experimental parameters on extraction conditions were studied. The linear range is from 2 to 1000 μg L-1 for the target compounds, and the LODs are between 0.72 and 1.38 μg L-1. The relative recoveries range from 95 to 108% for river water; 96–109% for lake water and 86–114% for irrigating water.

    摘要 i Abstract ii 謝誌 iii 目錄 iv 表目錄 viii 圖目錄 ix 第一章 緒論 1 1.1 前言 1 1.2 各種微萃取方法 2 1.2.1 固相微萃取 (solid-phase microextraction, SPME) 2 1.2.2 單滴微萃取 (single-drop microextraction, SDME) 3 1.2.3 中空纖維液相微萃取 (hollow fiber protected liquid phase microextraction, HF-LPME) 4 1.2.4 溶劑棒微萃取 (solvent bar microextraction, SBME) 5 1.2.5 分散式液液微萃取法 (dispersive liquid-liquid microextraction, DLLME) 6 1.2.6 冷凝液液微萃取法 (liquid-phase microextraction method based on solidification of floating organic drop) 8 1.2.7 冷凝分散式液液微萃取法 (dispersive liquid-liquid microextraction method based on solidification of floating organic drop, DLLME-SFO) 9 1.2.8 超音波輔助乳化微萃取 (ultrasound-assisted emulsification microextraction, USAEME) 10 1.2.9 少量溶劑分散式液液微萃取法 (dispersive liquid-liquid microextraction with little solvent consumption, DLLME-LSC) 11 1.2.10 vortex輔助液液微萃取法 (vortex-assisted liquid-liquid microextraction, VALLME) 11 1.2.11 vortex輔助界面活性劑增強乳化液液微萃取 (vortex-assisted surfactant enhanced emulsification liquid-liquid microextraction, VSLLME) 12 1.2.12 特製離心管改善溶劑收集 13 1.2.13 溶劑終結乳化分散式液液微萃取法 (solvent-based solvent terminated dispersive liquid-liquid microextraction, ST-DLLME) 14 1.2.14 針內超音波輔助乳化微萃取 (in-syringe ultrasound-assisted emulsification microextraction) 15 1.3 研究目的 16 第二章 實驗部分 17 2.1 實驗藥品 17 2.1.1 分析物標準品 17 2.1.2 萃取溶劑 18 2.1.3 界面活性劑 18 2.1.4 其它試劑 18 2.2標準溶液 19 2.3 環境樣品 20 2.4 實驗儀器裝置 20 2.4.1 實驗裝置 20 2.4.2實驗儀器 21 2.4.3儀器操作條件 21 2.5 實驗步驟 22 2.5.1 垂直震盪器輔助乳化 22 2.5.2 界面活性劑輔助乳化 24 第三章 結果與討論 26 3.1 濃縮倍數與回收率 26 3.2 垂直震盪器輔助乳化的萃取條件最佳化 27 3.2.1 萃取溶劑種類 27 3.2.2 鹽類添加量 29 3.2.3 萃取溶劑體積 31 3.2.4 萃取時間 33 3.2.5 vortex輔助乳化時間 35 3.3 界面活性劑輔助乳化的萃取條件最佳化 37 3.3.1 萃取溶劑種類 37 3.3.2 界面活性劑種類 39 3.3.3 鹽類添加量 41 3.3.4 萃取溶劑體積 43 3.3.5 界面活性劑濃度 45 3.3.6 界面活性劑體積 47 3.4 三種方法比較 49 3.5 分析方法的表現 51 3.5.1 線性、偵測極限與濃縮倍數 51 3.5.2 再現性 53 3.5.3 環境樣品分析 54 3.5.4 分析方法的比較 63 第四章 結論 65 參考文獻 66

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