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研究生:馬姿蓉
研究生(外文):Tzu-Jung Ma
論文名稱:利用中空纖維液相微萃取同步針內衍生化技術配合GC-ECD分析水樣中苯氧酸系除草劑
論文名稱(外文):Determination of phenoxy acidic herbicides in environmental water by hollow fiber protected liquid phase microextraction coupled in-syringe derivatization and GC-ECD
指導教授:鄭政峯鄭政峯引用關係
指導教授(外文):Jen-Fon Jen
學位類別:碩士
校院名稱:國立中興大學
系所名稱:化學系所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2008
畢業學年度:96
語文別:中文
論文頁數:70
中文關鍵詞:苯氧酸系除草劑液相微萃取中空纖維管六氟異丙醇衍生化反應
外文關鍵詞:phenoxy acidic herbicidesliquid phase microextraction (LPME)hollow fiber (HF)111333-hexafluoro-2-propanol (HFIP)derivatization
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  苯氧酸系除草劑為有機氯農藥的一種,由於其羧酸之特性,易形成離子態,透過地表流逕或土壤淋洗作用而傳輸到地下水,進一步威脅飲用水安全。本研究開發對環境水樣品中的苯氧酸系除草劑綠色檢測法,研究中利用中空纖維液相微萃取同步針筒內衍生化技術配合GC-ECD分析水樣中苯氧酸系除草劑,檢測對象包括2,4-D、2,4,5-T、MCPP、MCPA。以10 μL注射針內預置衍生化試劑HFIP(1,1,1,3,3,3-hexafluoro-2-propanol)及催化劑DIC(N,N’-diisopropyl-carbodiimide),注射針尖端裝置內含乙酸己酯的中空纖維管為液相微萃取探針,對5 mL水樣品(添加鹽類濃度0.1 M,調整至pH 2.5),在870 rpm磁石攪拌、40 ℃水浴恆溫下萃取20 min後,將微萃取溶劑抽回針筒內,與衍生化試劑混合,進行反應,再以氣相層析儀附電子捕獲偵檢器(GC-ECD)分析。以本方法最佳條件分析2,4-D及2,4,5-T,其線性範圍在0.05-2 μg/L,MCPP及MCPA之線性範圍在0.2-10 μg/L,其相關係數在0.9962-0.9999之間。偵測極限分別為0.007 μg/L(2,4-D)、0.004 μg/L(2,4,5-T)、0.04 μg/L(MCPP)及0.03 μg/L(MCPA)。所發展之檢測技術,應用於環境湖水樣品,偵測到含有2,4,5-T濃度1.1 μg/L,回收率介於76-92%。
  In the present study, a noble analytical method for the determination of phenoxy acidic herbicides (2,4-D, 2,4,5-T, MCPA, and MCPP) has been investigated. This procedure combines the hollow fiber (HF) protected liquid phase microextraction (LPME) with an in-syringe derivatization. The sampling apparatus was assembled by a microsyringe pre-filled with derivatization agent, 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and N,N’-diisopropyl-carbodiimide (DIC), and then 1.5cm polypropylene hollow fiber filled with hexyl acetate (3.5 μL) was inserted into the needle for LPME extraction. The sample solution(5 mL)was prepared in 0.1 M NaCl and adjusted pH to 2.5 for LPME sampling at 40℃ (water bath and stirred with 870 rpm). The acidic herbicides were diffused through the hollow fiber and collected in hexyl acetate for 20 mins. After the extraction of these chemicals, derivatization was achieved through mixing the extraction solvent and derivatization agents. In the syringe barrel, before it was separated and detected using capillary gas chromatography with electron capture detector.
  Under the optimal conditions, the linear range for 2,4-D and 2,4,5-T were 0.05-2 μg/L, and for MCPP and MCPA were 0.2-10 μg/L. The correlation coefficients were between 0.9962-0.9999. The limit of detection were 0.007 μg/L for 2,4-D, 0.004 μg/L for 2,4,5-T, 0.04 μg/L for MCPP, and 0.03 μg/L for MCPA. In a real sample (lake water) analysis, 2,4,5-T was detected as 1.1 μg/L. The recovery of phenoxy acid herbicides in real sample was between 76-92%.
第一章 緒論……………………………………1
一、研究緣起………………………1
二、苯氧酸系除草劑之簡介………………………1
三、苯氧酸系除草劑分析樣品前處理技術………………………3
(一)液相-液相萃取法(Liquid-Liquid extraction, LLE)……3
(二)固相萃取法(Solid Phase Extraction, SPE)………………………4
(三)固相微萃取(Solid Phase Microextraction, SPME)………………………5
(四)液相微萃取法(Liquid Phase Microextractrion,LPME)…………9
四、苯氧酸系除草劑之衍生化反應………………………20
五、研究目的………………………22
第二章 試驗材料與研究方法………………………24
一、藥品、器材及儀器設備………………………24
(一)藥品………………………24
(二)器材及儀器設備………………………25
二、藥品配製………………………26
(一)四種不同苯氧酸除草劑標準品1000 mg/L個別儲存溶液之配製………26
(二)苯氧酸除草劑標準品100 mg/L和10 mg/L中間濃度溶液之配製………26
(三)直接注入法苯氧酸除草劑檢量線範圍濃度溶液之配製…………26
(四)HF-LPME針內衍生化方法苯氧酸除草劑檢量線範圍濃度溶液之配製………26
(五)試藥之配製………………………26
(六)真實樣品………………………27
三、玻璃器皿的矽烷化………………………27
四、試驗儀器及條件設定………………………27
五、實驗裝置與步驟 ………………………28
(一)直接衍生化………………………28
(二)HF-LPME暨衍生化方法裝置與步驟………………………28
六、實驗條件探討………………………32
(一)萃取中空纖維管的選擇………………………32
(二)注射針與中空纖維管之組合及萃取步驟………………………32
(三)萃取溶劑之選擇………………………32
(四)萃取溫度之探討………………………33
(五)萃取時間之探討………………………33
(六)樣品pH值之探討………………………33
(七)鹽析效應之探討………………………33
(八)衍生化試劑取用量之探討………………………34
(九)衍生化反應混合次數之探討………………………34
(十)樣品攪拌速率之探討………………………34
(十一)水溶液中苯氧酸除草劑之濃度範圍、校正曲線方程式、相關係數及偵測極限………………………34
(十二)精密度探討………………………35
七、真實樣品的測定………………………35
八、真實樣品回收率的確認………………………35
第三章 結果與討論………………………36
一、HF-LPME暨衍生化反應之最佳化條件探討………………………36
(一)中空纖維管長度之選擇………………………36
(二)萃取溶劑之選擇………………………36
(三)萃取溫度之影響………………………39
(四)萃取時間之影響………………………39
(六)鹽析效應之影響………………………42
(七)衍生化試劑取用量之探討………………………45
(八)混合次數對衍生化反應之影響………………………45
(九)樣品攪拌速率………………………48
二、方法可行性之評估………………………50
(一)校正曲線及偵測極限………………………50
(二)精密度試驗………………………50
(三)濃縮倍率………………………54
(四)真實樣品之分析………………………55
三、氣相層析質譜儀鑑定………………………57
四、與現有方法之比較………………………63
第四章 結論………………………65
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