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研究生:張娣安
研究生(外文):Ti-Ann Chang
論文名稱:以固相微萃取技術發展空氣中戊醛之被動式採樣器
論文名稱(外文):A passive sampler for valeraldehyde in air based on solid phase microextraction
指導教授:蔡詩偉蔡詩偉引用關係
指導教授(外文):Shih-Wei Tsai
學位類別:碩士
校院名稱:中國醫藥學院
系所名稱:環境醫學研究所
學門:醫藥衛生學門
學類:公共衛生學類
論文種類:學術論文
論文出版年:2001
畢業學年度:89
語文別:中文
論文頁數:75
中文關鍵詞:固相微萃取五氟芐羥胺戊醛被動式採樣器氣相層析
外文關鍵詞:SPMEPFBHAAldehydesPassive SamplerGas Chromatography
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醛類廣泛地被使用於工作場所中做為殺菌劑、滅菌劑、防腐劑、組織固定劑及黏著劑等;在環境中,諸如燃料燃燒、抽煙的煙燻及水的臭氧化處理等,亦存在醛類的污染。醛類是黏膜刺激物,暴露後會影響肺部,皮膚,眼睛,甚至中樞神經系統;另外,包括甲醛,乙醛,喃甲醛,及反丁烯-2-醛等是確定的動物致癌物質,而甲醛更是疑似人類致癌物質。由於醛類幾乎無所不在,而且經暴露會造成明顯的健康危害,因此是需要一個準確、快速、方便的醛類暴露評估方法。
本研究以戊醛為研究對象,設計被動式採樣器,並希望能將成果應用於其他醛類上。採樣器以固相微萃取(Solid Phase Microextraction, SPME)的熔融矽纖維為主體,再置於鐵弗龍管中;整個採樣器長約13.5cm、重約 8.73g、 擴散面積0.00086cm^2、擴散徑長0.3cm。所使用的熔融矽纖維材質為poly(dimethylsiloxane) /divinylbenzene (PDMS/DVB),並裹附五氟芐羥胺(O-2,3,4,5,6- (pentafluorobenzyl) hydroxylamine hydrochloride, PFBHA),構成採樣介質。
設計完成之採樣器,分別利用空氣採樣袋及動態暴露評估系統進行擴散式被動採樣評估;樣品採集完成後,直接以氣相層析儀火燄離子偵測器進行熱脫附及分析,分析時之標準曲線則以實驗合成之oxime 製備。
固相微萃取之熔融矽纖維以頂空法萃取裹附五氟芐羥胺之條件,經實驗決定以轉速1100 rpm進行兩分鐘;樣本熱脫附之條件為250°C兩分鐘;分析方法偵測戊醛的極限為27 ng;經空氣採樣袋評估的結果,採樣器的實驗採樣率為(3.66 ± 0.25)*10^-2 cm^3/min、經動態標準氣體製造系統評估的結果則為(3.93 ±0.16)*10^-2 cm^3/min;採樣器的表現並不會受到風速的影響,而其他可能影響採樣器的因素,如:溫度、濕度、採樣時間、採樣器壽命、及樣本保存期限等,皆於文中有所討論。

Aldehydes are widely used industrial chemicals and are also encountered in the ambient environment as a result of fuel combustion, other combustion process and oxidative reactions of organics. Exposed to aldehydes will cause pulmonary, skin, eye and central nervous system effects because they are mucous membrane irritants. Some aldehydes, including formaldehyde, acetaldehyde, furfural, and crotonaldehyde are animal carcinogens, and formaldehyde is a suspected human carcinogen. Since aldehydes are almost everywhere and the exposures of aldehydes will cause significant health effects, an accurate, fast and convenient method for sampling and analysis is needed for the purpose of exposure assessment.
The aim of this research is to develop a new passive sampler for alehydes in air based on the technique of solid phase microextraction (SPME) and the use of O-2,3,4,5,6-(pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA). The poly(dimethylsiloxane)/divinylbenzene (PDMS/DVB) fiber was used, and the fiber assembly was put into a Teflon tubing to construct the sampler. The weight of the designed passive sampler was 8.73 g with the length of 13.5 cm. The diffusion path of the sampler was 0.3 cm and the cross- area was 0.00086 cm2. Dynamic standard-gas- generation system and air sampling bag were both used for sampler evaluations. After sampling, the sample was analyzed directly by GC-FID for thermal desorption and quantification. The standard solutions for sample analysis were made from the oximes synthesized.
The appropriate loading time for SPME coating PFBHA was determined to be 2 min at 1100 rpm and the desorption time for oxime formed after sampling was optimized to be 2 min at 250°C. The experimental sampling constants were found to be (3.66 ± 0.25)*10^-2 cm^3/min from the exposures of air bags and (3.93 ±0.16)*10^-2 cm^3/min from dynamic standard gas generation system. The air velocity was found to have no effect on the performance of the sampler while other factors including temperature, relative humidities, sampling time, shelf life and sample stability were also discussed.

第1章 研究概述..............................................1
第1節 研究動機……………………………………………………………1
第2節 研究目的……………………………………………………………2
第3節 研究架構……………………………………………………………3
第2章 文獻探討..............................................4
第1節 醛類…………………………………………………………………4
2-1.1 理化性質 4
2-1.2 環境流佈與用途 4
2-1.3 健康危害性 5
2-1.4 容許暴露標準 6
2-1.5 採樣與分析 7
2-1.6 醛類與五氟芐羥胺之衍生反應 9
第2節 被動式採樣器………………………………………………………10
2-2.1 定義 10
2-2.2 採樣原理 10
2-2.3 主動式與被動式採樣之比較 11
2-2.4 影響因素與限制 12
2-2.5 被動式採樣採集醛類之相關研究 13
第3節 固相微萃取技術……………………………………………………14
2-3.1 緣起 14
2-3.2 免溶劑技術 14
2-3.3 固相微萃取之裝置設備 16
2-3.4 固相微萃取之理論 17
2-3.5 固相微萃取之應用 20
2-3.6 小結 21
第3章 材料與方法..............................................22
第1節 實驗器材……………………………………………………………22
3-1.1藥品試劑 22
3-1.2儀器設備 22
第2節 採樣器製備…………………………………………………………25
3-2.1 選擇採樣介質 25
3-2.2 衍生試劑之裹附 25
3-2.3 熱脫附之條件 25
第3節 戊醛蒸氣暴露評估…………………………………………………27
3-3.1 採樣對象之選取 27
3-3.2 暴露評估環境條件之設定 27
3-3.3 空氣採樣袋之使用 28
3-3.4 動態暴露評估系統 29
3-3.5 動態標準氣體產生 29
第4節 分析方法……………………………………………………………31
3-4.1 標準曲線製作 31
3-4.2 儀器分析條件 31
3-4.3 偵測極限 32
第4章 結果..............................................33
第1節 被動式採樣器雛形……………………………………………………33
第2節 五氟芐羥胺裹附與熱脫附條件之建立………………………………34
4-2.1 五氟芐羥胺裹附試驗結果 34
4-2.2 熱脫附條件之建立 34
第3節 戊醛蒸氣暴露評估……………………………………………………36
4-3.1 空氣採樣袋 36
4-3.2 動態暴露評估系統 36
第5章 討論 .............................................. 38
第1節 採樣器的設計……………………………………………… 38
第2節 裹附條件的決定………………………………………………………39
第3節 與其他醛類被動式採樣器的比較……………………………………40
第4節 被動式採樣器之影響因素…………………………………………41
5-4.1 理論採樣率與實驗採樣率的差異 41
5-4.2 濕度 42
5-4.3最小界面風速 43
5-4.4 採樣器的壽命及樣本保存期限 43
5-4.5 採樣器的反應時間 44
第6章 結論與建議..............................................45
參考文獻 46
表列 57
圖列 63
附錄 73
附錄一 戊醛─五氟芐羥胺衍生物之合成方法 73
附錄二 固相微萃取之萃取纖維前處理 74
表 目 錄
表2-1 醛類之理化性質………………………………………………………57
表2-2 醛類之暴露容許濃度…………………………………………………58
表2-3 醛類之採樣分析方法…………………………………………………59
表2-4 採樣器性能之影響因素………………………………………………60
表2-5 固相微萃取萃取纖維參考表(氣相層析儀使用)…………………61
表4-1 五氟芐羥胺裹附與熱脫附試驗結果…………………………………62
圖 目 錄
圖2-1 固相微萃取裝置圖……………………………………………………63
圖2-2 固相微萃取取樣與進樣程序…………………………………………64
圖3-1 動態暴露系統示意圖…………………………………………………65
圖3-2 動態暴露腔示意圖……………………………………………………65
圖4-1 被動式採樣器性能之雛形……………………………………………66
圖4-2(a) 五氟芐羥胺之標準曲線…………………………………………67
圖4-2(b) oxime之標準曲線…………………………………………………67
圖4-3 五氟芐羥胺裹附量與裹附時間之關係………………………………68
圖4-4 脫附效率與脫附時間之關係…………………………………………68
圖4-5(a) oxime標準曲線層析圖譜…………………………………………69
圖4-5(b) 被動式採樣採集戊醛後熱脫附分析之層析圖譜………………70
圖4-6 採樣率測試結果─空氣採樣袋………………………………………71
圖4-7採樣率測試結果─動態暴露評估系統………………………………71
圖5-1 SUPELCO 固相微萃取現場採樣器……………………………………72

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