臺灣博碩士論文加值系統

二甲基硫(dimethyl sulfide, DMS)和二甲基二硫(dimethyl disulfide, DMDS)是具有臭味的揮發性硫化物，主要源自含硫有機物質厭氧分解。高濃度會刺激呼吸道、眼睛和皮膚，大量暴露可能導致意識喪失，並且為易燃性物質，曾為局限空間工作者致死之有毒氣體之一，因此倍受關心。本研究採用固相微萃取裝置(solid phase microextraction, SPME)搭配可攜式氣相層析儀，對於二甲基硫(dimethyl sulfide, DMS)和二甲基二硫(dimethyl disulfide, DMDS)進行採樣與分析之研究，以方便緊急時進行現場快速偵測。本研究使用Tedlar bag製備DMS和DMDS參考氣體，將袋中硫化物參考氣體濃度控制為三個等級(level)，氣體相對濕度控制為六個等級，每個試驗進行三重複。選用纖維材質為75μm CarboxenTM-PDMS fiber，配合SPME裝置，進行裸露方式的採樣，採樣後之SPME纖維瞬即插入可攜式氣相層析儀之管柱(MXT-1)熱脫附分析，同時以檢知管法進行方法的比較。結果顯示兩種硫化物的採樣和分析可以在12分鐘內完成；裹覆厚度為75μm的CarboxenTM-PDMS fiber對於DMS的最大附載質量為27.57ng，而對DMDS的最大附載質量為5.12ng。當氣體相對濕度超過43.6％，採集質量會有較明顯的下降，而且相對濕度和硫化物濃度彼此也有交互作用。檢知管檢測DMS之準確度為1.5％∼133.9％，精密度為4.0％∼19.3％；而SPME/Portable GC/FPD檢測DMS之準確度則為1.8％∼52.2％，精密度為0.3％∼2.1％。

摘要 Ⅰ
Abstract Ⅱ
致謝 Ⅲ
目錄 Ⅳ
表目錄 Ⅶ
圖目錄 Ⅷ
第一章 緒論 1
1-1 前言 1
1-2 研究目的 2
1-3 研究架構 3
第二章 文獻探討 4
2-1 局限空間介紹 4
2-2 局限空間的危害 4
2-3 局限空間作業危害預防 7
2-4 硫化物介紹及其毒性資料 7
2-5 空氣中硫化物採樣分析方法 11
2-6 固相微萃取技術 16
2-7 可攜式氣相層析儀 22
2-8 固相微萃取技術與可攜式氣相層析儀的結合 24
2-9 火焰光度偵檢器與硫化物的檢測 25
2-10 實驗設計法 25
第三章 材料與方法 27
3-1 儀器設備與試藥 27
3-1-1 儀器設備與材料 27
3-1-2 試劑耗材 29
3-2 標準溶液的製備 29
3-3 檢量線的製作 30
3-4 樣品穩定性測試 31
3-5 參考氣體產生系統 31
3-5-1 稀釋空氣淨化裝置 32
3-5-2 稀釋空氣流量率控制裝置 32
3-5-3 濕度控制與量測 32
3-5-4 硫化物氣體濃度之控制 33
3-6 參考氣體產生系統驗證 34
3-6-1 浮子流量計之校準 34
3-6-2 相對濕度控制之驗證 34
3-7 SPME採樣分析硫化物之驗證 35
3-8 熱脫附效率測試 36
3-9 SPME採樣時間測試 36
3-10 不同硫化物濃度不同相對濕度下檢知管的採樣 37
第四章 結果 38
4-1 分析之品管 38
4-1-1 GC對硫化物的定性 38
4-1-2 DMS和DMDS檢量線 38
4-1-3 樣品穩定性測試 38
4-2 參考氣體產生系統品管 39
4-2-1 氣體流量率控制 39
4-2-2 相對濕度之控制 39
4-3 SPME採樣分析硫化物之驗證 39
4-3-1 熱脫附條件測試 39
4-3-2 SPME採樣時間測試 40
4-4 各控制變項對於SPME採樣表現的影響 41
4-5 各控制變項對於檢知管採樣表現的影響 42
第五章 討論和建議 44
5-1 SPME對於參考氣體採樣的探討 44
5-2 檢知管對於參考氣體採樣的探討 50
參考文獻 54

表目錄
表2-1 DMS的物理化學基本特性 60
表2-2 DMDS的物理化學基本特性 60
表2-3 現今空氣中DMS和DMDS分析方法整理 61
表2-4 現今SPME採樣分析DMS與DMDS之研究整理 62
表2-5 不同纖維材質的種類 64
表4-1 SPME採集DMS與DMDS熱脫附效率測試結果 64
表4-2 SPME對DMS之採集量與採樣時間的關係 65
表4-3 SPME對DMDS之採集量與採樣時間的關係 66
表4-4 SPME採集DMS質量與DMS濃度及相對濕度的關係 67
表4-5 DMS濃度和相對濕度影響SPME對DMS採集質量變異數分析
(Two way ANOVA)結果 68
表4-6 SPME採集DMDS質量與DMDS濃度及相對濕度的關係 69
表4-7 DMDS濃度和相對濕度影響SPME對DMDS採集質量變異數分析
(Two way ANOVA)結果 70
表4-8 不同DMS濃度不同相對濕度下檢知管的採樣分析結果 71
表4-9 SPME採集DMS採樣率與DMS濃度及相對濕度的關係 72
表4-10 不同DMS濃度不同相對濕度下SPME/GC的採樣分析結果 73

圖目錄
圖2-1 風箱式檢知器 75
圖2-2 膠球式檢知器 75
圖2-3 活塞式檢知器 75
圖2-4 單層式檢知管 76
圖2-5 多層式檢知管 76
圖2-6 雙生式檢知管 76
圖2-7 現今水中與空氣中揮發性硫化物之採樣分析流程 77
圖2-8 固相微萃取裝置 78
圖2-9 SPME纖維裸露採樣示意圖 78
圖3-1 參考氣體產生系統 79
圖3-2 氣體濕度與溫度量測控制系統 79
圖4-1 二甲基硫(DMS)在GC/FPD上的分析圖譜 80
圖4-2 二甲基二硫(DMDS)在GC/FPD上的分析圖譜 80
圖4-3 二甲基硫(DMS)之檢量線 81
圖4-4 二甲基二硫(DMDS)之檢量線 81
圖4-5 二甲基硫(DMS)樣品穩定性測試 82
圖4-6 二甲基二硫(DMDS)樣品穩定性測試 82
圖4-7 浮子流量計(FJS-110319-F, Taiwan)流量率之檢量線 83
圖4-8 注水量與袋中相對濕度的關係 83
圖4-9 用SPME (75μm CarboxenTM-PDMS fiber)採DMS之採集量
與採樣時間的關係 84
圖4-10 用SPME(75μm CarboxenTM-PDMS fiber)採DMDS之採集量
與採樣時間的關係 84
圖4-11 用SPME(75μm CarboxenTM-PDMS fiber)採DMS之採集量
與相對濕度及DMS濃度的關係 85
圖4-12 用SPME(75μm CarboxenTM-PDMS fiber)採DMDS之採集量
與相對濕度及DMDS濃度的關係 85
圖4-13 不同DMS濃度不同相對濕度下檢知管的採樣結果 86
圖4-14 不同DMS濃度不同相對濕度下SPME的採樣結果 86
圖4-15 SPME/GC檢出濃度與檢知管讀出濃度的關係 87

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