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研究生: 張家瑜
Chia-yu Chang
論文名稱: 以震盪輔助式液液微萃取法檢測水樣中的短鏈氯化石蠟
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
論文出版年: 2015
畢業學年度: 103
語文別: 中文
論文頁數: 126
中文關鍵詞: 短鏈氯化石蠟震盪輔助式液液微萃取法氣相層析電子捕捉負離子質譜儀
外文關鍵詞: SCCPs, VALLME, GC/ECNI-MS
相關次數: 點閱:22下載:0
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  • 短鏈氯化石蠟(short chain chlorinated paraffins, SCCPs) 是指碳鏈長度為10 至13 且氯含量介於30%至72%之間的直鏈氯化烷烴。
    短鏈氯化石蠟具有持久性、生物累積性以及經由大氣進行遠距離遷移
    的能力,斯德哥爾摩公約(Stockholm Convention) 目前也擬將短鏈氯
    化石蠟增列為優先控制之持久性有機物染物(persistent organic
    pollutants, POPs)。因此開發一套簡單、有效率且穩固的方法來檢測環
    境中的短鏈氯化石蠟是勢在必行的。
    本研究以震盪輔助式液液微萃取法(vortex-assisted liquid-liquid
    microextraction, VALLME) 為前處理方法,並搭配氣相層析電子捕捉
    負離子質譜儀(GC/ECNI-MS) 對水樣中的短鏈氯化石蠟進行檢測。
    震盪輔助式液液微萃取法的最佳化條件為:取400 μL 的二氯甲烷
    快速注入20 mL 的水樣中,接著使用多功能震盪機以2500 rpm 高速
    震盪1 分鐘,再以4500 rpm 的轉速離心3 分鐘,使有機層與水層分
    離,隨後取出有機沉澱相並以吹氮回溶至10 μL,最終取1 μL 進樣於
    GC/ECNI-MS 進行分析。偵測極限(limit of detection, LOD) 為0.02
    μg/L。在inter-days 及intra-day 的測試中,其所得相對標準偏差(RSDs)
    皆小於9%,顯示本方法具有良好的再現性與穩定性。在國內不同水
    樣中所測得的短鏈氯化石蠟濃度為0.08 至0.16 μg/L。


    Short chain chlorinated paraffins (SCCPs) are polychlorinated n-alkanes with carbon chain lengths from 10 to 13 and a chlorination degree between 30 and 72% by mass. SCCPs are resistant to environmental degradation and also have characteristics such as bioaccumulation and long-range transport. A global ban on SCCPs is being considered under the Stockholm Convention on Persistent Organic Pollutants, so it is necessary to develop a simple, efficient and robust method to monitor SCCPs in the environment.
    In this study, vortex-assisted liquid-liquid microextraction (VALLME) coupled with GC/ECNI-MS was developed and used to determine SCCPs in water samples. The optimized procedure of VALLME were as follows: 400 μL of dichloromethane was rapidly injected into a 20 mL water
    sample. After vortex for 1 min at 2500 rpm and centrifugation for 3 min at 4500 rpm, the mixture became a two-phase solution. Then the sedimented phase was transferred to the vial and evaporated to dryness by a gentle stream of nitrogen. Prior to analysis, 10 μL of acetone containing internal standard was added in the vial and 1μL was injected into
    GC/ECNI-MS for analysis.We also used a method termed vortex-assisted enrichment-enhanced liquid-liquid microextraction (VAEELLME) in the analysis of real water samples.With this method, we can obtain higher enrichment and lower detection limit.
    The limit of detection (LOD) for SCCPs in water samples was determined to be 0.02 μg/L. The relative standard deviations (RSDs) of inter-days and intraday tests were lower than 9% and the SCCPs levels in water samples ranged from 0.08 to 0.16 μg/L.

    摘要 I Abstract III 謝誌 V 目錄 VI 圖目錄 VIII 表目錄 X 第一章 前言 1 1-1 研究緣起 1 1-2 研究目標 3 第二章 文獻回顧 5 2-1 氯化石蠟 5 2-1-1 性質 5 2-1-2 用途及生產量 7 2-1-3 毒性研究 8 2-1-4 環境流布 9 2-1-4-1 降解 9 2-1-4-2 生物累積 10 2-1-4-3 遷移 11 2-2 國外相關研究 12 2-3 氣相層析質譜儀 19 2-3-1 四極矩質譜儀 21 2-3-2 電子捕捉負離子游離法 22 2-3-3 選擇離子偵測模式 24 2-4 分散式液液微萃取法 25 2-4-1 前言 25 2-4-2 原理 26 2-4-3 萃取流程 27 2-4-4 影響因素 28 2-4-4-1 萃取劑種類 28 2-4-4-2 分散劑種類 28 2-4-4-3 萃取劑體積 29 2-4-4-4 分散劑體積 29 2-4-4-5 萃取時間 29 2-4-4-6 鹽類添加 29 2-4-5 發展 30 2-5 震盪輔助式液液微萃取法 35 2-6 線性回歸 36 2-6-1 Mandel test 36 2-6-2 The lack-of-fit test by ANOVA 38 2-7 基質效應 40 第三章 實驗步驟與樣品分析 43 3-1 實驗藥品與設備 43 3-1-1 實驗藥品 43 3-1-2 儀器設備 45 3-2 實驗步驟 46 3-2-1 標準品的配置 46 3-2-2 氣相層析質譜儀的參數設定 47 3-2-3 分散式液液微萃取法 (DLLME) 49 3-2-4 超音波乳化液液微萃取法 (USAEME) 50 3-2-5 震盪輔助式液液微萃取法 (VALLME) 51 3-3 水樣採集 53 第四章 結果與討論 55 4-1 氣相層析質譜儀對短鏈氯化石蠟的測定 55 4-1-1 短鏈氯化石蠟的分析 55 4-1-2 短鏈氯化石蠟的定性與定量 59 4-1-3 檢量線與偵測極限 59 4-2 液液微萃取法之比較 61 4-3 震盪輔助式液液微萃取法之最佳化探討 62 4-3-1 萃取劑的種類 62 4-3-2 萃取劑的體積 64 4-3-3 震盪的轉速 65 4-3-4 震盪的時間 66 4-3-5 水樣的pH值 67 4-3-6 震盪輔助式液液微萃取法的最佳化結果 68 4-4 線性方程式的適用性 69 4-4-1 Mandel Test 69 4-4-2 The lack-of-fit test by ANOVA 70 4-5 真實樣品的檢測 71 4-5-1 放流水樣品 71 4-5-2 溪水樣品 75 4-5-3 檢測結果之比較 77 4-5-4 基質效應 79 4-6方法的精密度及準確度 80 第五章 結論 81 第六章 參考文獻 83 附錄 99

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