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研究生:黃琬淑
研究生(外文):Wu-Sue Huang
論文名稱:微波輔助頂空固相微萃取技術結合氣相層析法應用於樣品中多溴二苯醚之偵測
論文名稱(外文):Application of Microwave assisted headspace solid phase microextraction coupled to GC-ECD to determine polybrominated diphenyl ethers
指導教授:鄭政峰鄭政峰引用關係
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:93
中文關鍵詞:微波輔助固相微萃取多溴二苯醚氣相層析儀-電子捕捉偵測器
外文關鍵詞:Polybrominated diphenyl ethers (PBDEs)microwave assistedheadspace solid phase microextraction
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多溴二苯醚常被添加於電子材料、紡織品及建築材料中,用為火焰阻燃劑。由於屬添加型的阻燃劑,容易釋放於生活環境中,對環境及人體都有莫大的影響。多溴二苯醚的檢測方法,傳統使用的萃取方法常需要花很長的時間及大量有機溶劑,對於分析方法的綠色需求來說不盡理想,因此發展一個新的分析技術來加以改進是重要的課題。
本研究利用微波輔助頂空固相微萃取結合氣相層析電子捕捉偵測器(GC-ECD)分析多溴二苯醚在樣品中的含量。本實驗目標分析物為BDE-28、47、99、100、153、154、183、209。在管柱選擇方面,BDE-28、47、99、100、153、154、183使用的為HP-5ms(30m,0.25mm I.D,0.25μm)毛細管管柱,BDE-209則使用長度較短且厚度較薄的DB-5ms(15m,0.25mm I.D,0.1μm)之管柱 。
實驗中使用10mL樣品量來進行最佳化條件探討,分別探討纖維塗佈材質,微波照射時間、功率,頂空採樣系統溫度及脫附時間、溫度,樣品pH及鹽類添加等最佳化條件。結果顯示,BDE-28、47、99、100、153、154、183七種多溴二苯醚,最佳化條件為使用100μm PDMS固相微萃取纖維,採樣溫度固定在10℃,以微波功率177瓦照射30分鐘,完成後,在GC注射口以300℃脫附4分鐘進行GC-ECD分析。偵測線性範圍BDE-28為O.05-5 ng/L,BDE-47、99、100、153、154為0.1-10 ng/L及BDE-183為5-500ng/ L,偵測極限為0.01-1ng/L之間,相關係數皆在0.99以上。
BDE-209(十溴二苯醚)最佳化條件為使用100μm PDMS固相微萃取纖維,冷凝溫度固定在10℃,以微波功率210瓦照射30分鐘,完成後,在GC注射口以300℃脫附5分鐘進行GC-ECD分析。偵測線性範圍為10-800ng/L,偵測極限為2ng/L,相關係數在0.99以上。
為驗證本方法的可行性,應用此技術於真實樣品中,成功的偵測於工廠廢水中、疏水性紡織布及ABS、PMMA樹脂中含有BDE-209。工廠廢水回收率試驗,可得回收率為77%~95%之間。利用微波輔助頂空固相微萃取技術結合氣相層析法偵測多溴二苯醚,具有快速、操作簡便、不受基質干擾及無需使用有機溶劑等優點,且方法具有良好的靈敏度,並可以很順利的偵測樣品中多溴二苯醚。微波輔助萃取針對高沸點分析物可以有效縮短萃取的時間,並且結合頂空固相微萃取可以降低樣品中基質干擾,有效的降低偵測極限。
A modified headspace solid-phase micro-extraction (HS-SPME) method was studied for the extraction of polybrominated diphenyl ethers (PBDEs) from aqueous samples, before gas chromatographic (GC) analysis with electron capture detection (ECD). Microwave heating was applied to accelerate the evaporation of PBDEs into the headspace, and an external-cooling system was used to control the sampling temperature. Conditions influencing extraction efficiency, such as the SPME-fibers, the sampling temperature, microwave power, and irradiation time (the same as sampling time), sample pH, and salt addition were thoroughly optimized. Experimental results indicated that the extraction of PBDEs from a 10-mL aquatic sample was achieved with the best efficiency through the use of 100 μm PDMS fiber, microwave irradiation of 171 W for BDE-28, 47, 99, 100, 153, 154 and 183 (210W for BDE-209), sampling at 10 oC for 30 min. The detections were linear in the concentration of 0.05 – 5 ng/L for BDE-28, 0.1 - 10 ng/L for BDE-47, 99, 100, 153, 154, 5 - 500 ng/L for BDE-183, 10 - 800 ng/L for BDE-209, respectively. Detection limits were found to be 0.01 - 0.03 ng/L (1ng/L for BDE-183 and 2 ng/L for BDE-209). Sample of industrial wastewater was analyzed with recovery between 77 – 95%. Cloth and polymers of ABS and PMMA were also analyzed. The present method was proven to serve as a simple, sensitive, and rapid procedure for PBDEs analysis in an aqueous sample as well as clothes and polymers.
摘要 i
ABSTRACT ii
目錄 iii
圖目錄 v
表目錄 vi
第一章 緒論 1
一、 多溴二苯醚的介紹 1
二、 多溴二苯醚分析樣品前處理技術 4
(一)液相-液相萃取 6
(二)索式萃取技術 6
(三)固相萃取法 7
(四)固相微萃取法 7
三、 微波加熱原理 17
(一)離子傳動 19
(二)偶極轉動 19
(三)微波源功率的輸出與計算 19
(四)微波加熱方式和傳統加熱方式的比較 21
(五)微波在化學反應中的功能 21
四、 研究目的 21
第二章 試驗材料及研究方法 26
一、藥品、器材及儀器設備 26
(一)藥品 26
(二)器材及儀器設備 27
二、 藥品配置 28
三、 玻璃器皿的矽烷化 31
四、 氣相層析儀條件之設定 32
五、 固相微萃取纖維之活化 32
六、 微波輔助頂空固相微萃取裝置之建立 32
七、 實驗步驟及最佳化條件探討 35
(一)微波輔助頂空固相微萃取實驗步驟 35
(二)固相微萃取纖維種類探討 35
(三)最佳微波照射條件探討 35
(四)樣品pH值探討 36
(五)鹽類添加探討 37
(六)固相微萃取纖維熱脫附條件探討 37
(七)水溶液中多溴二苯醚之校正曲線範圍、校正曲線方程式、校正曲線相關係數及偵測極限值的探討 38
(八)方法精密度探討 39
(九)真實樣品測定 40
(十)真實樣品回收率探討 40
(十一)它種樣品之應用 40
第三章 結果與討論 41
一、氣相層析儀條件與分離管柱之選擇 41
二、 微波輔助頂空固相微萃取最佳化條件探討 51
(一)固相微萃取纖維種類選擇 51
(二)最佳微波照射條件探討 54
1.微波功率的探討 54
2. 微波照射時間的探討 57
3. 冷凝系統溫度的影響 60
(三)樣品pH值探討 63
(四)鹽類添加探討 63
(五)固相微萃取纖維熱脫附條件探討 68
1. 熱脫附溫度探討 68
2. 熱脫附時間探討 71
三、方法可行性之評估 74
(一)校正曲線及偵測極限 74
(二)精密度探討 78
四、真實樣品之分析 80
(一)直接檢測 80
(二)以添加方式檢測 80
五、他種樣品應用 80
六、與現有方法比較 80
第四章 結論 87
第五章 參考文獻 88
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