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研究生:顏俊賢
研究生(外文):CHUN-HSIEN YEN
論文名稱:利用乙基化衍生反應配合吹氣捕捉濃縮裝置∕氣相層析儀—脈衝火焰光度偵測器分析水樣中有機錫含量之研究
論文名稱(外文):Speciation of Organotin Compounds in Water Samples by Purge and Trap Concentrator-GC-PFPD after Ethylation with Sodium Tetraethylborate
指導教授:王維賢
指導教授(外文):WEI-HSIEN WANG
學位類別:碩士
校院名稱:國立中山大學
系所名稱:海洋資源學系研究所
學門:自然科學學門
學類:海洋科學學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:87
中文關鍵詞:四乙基硼化鈉有機錫
外文關鍵詞:organotinsodium tetraethylborate
相關次數:
  • 被引用被引用:3
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  • 下載下載:23
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中文摘要
本研究利用四乙基硼化鈉之乙基化衍生反應配合吹氣捕捉濃縮裝置/氣相層析儀—脈衝火焰光度偵測器分析水樣中有機錫化合物,於樣本玻璃管中加入5.5 ml水樣、1.5 ml衍生化試劑及2 ml緩衝溶液,然後裝妥於吹氣捕捉濃縮裝置,隨後所有的分析步驟包括乙基化反應、吹氣捕捉濃縮、層析分離及偵測即完全以自動化進行;影響本分析方法之因素包括四乙基硼化鈉溶液的濃度、吹氣流速、吹氣時間、脫附時間、緩衝溶液pH值、脈衝火焰光度偵測器之氫氣流速及其光電倍增管電壓皆為最佳化條件。本分析方法對於二丁基錫及三丁基錫的偵測極限分別為0.50及0.46 ng as Sn/L,兩者的檢量線線性範圍皆達到2個級數。應用此分析方法測量高雄港十四個不同位置之表層水體中有機錫化合物的濃度及測量樣品回收率,結果二丁基錫的濃度範圍從低於方法偵測極限至272.2 ng as Sn/L,三丁基錫的濃度範圍從低於方法偵測極限至105.4 ng as Sn/L,兩者的回收率則介於88.9∼95.3 %。
ABSTRACT
A purge and trap concentrator coupled to gas chromatography-pulsed flame photometric detector(GC-PFPD) after in situ ethylation with sodium tetraethylborate(NaBEt4) was used to analyze organotin compounds in water samples. The sample glassware with 5.5 ml water sample, 1.5 ml derivatizing reagent as well as 2 ml buffer solution was installed to purge and trap system, and then all steps were performed automatically, including ethylation, purge and trap, concentration, chromatography seperation and detection. Parameters including NaBEt4 concentration, purge flow rate, purge time, desorb time, the pH of buffer solution, H2 flow rate and the voltage of photomultiplier tube(PMT) of PFPD , which influence the speciation of organotin compounds were optimized. Method detection limits for dibutyltin and tributyltin were 0.50 and 0.46 ng as Sn/L, respectively. The calibration graphs were linear up to 2 orders of magnitude. Surface water samples collected from fourteen different locations of Kaohsiung harbor were analyzed. The concentration of dibutyltin ranged from nondetected(ND) to 272.2 ng as Sn/L and tributyltin ranged from nondetected to 105.4 ng as Sn/L. Recovery percentage for dibutyltin and tributyltin ranged from 88.9-95.3 %.
目 錄
頁次
中文摘要………………………………………………………………1
英文摘要………………………………………………………………2
壹、前言………………………………………………………………3
一、有機錫化合物發展的歷史及用途………………………………3
二、有機錫化合物的生物活性及毒性………………………………5
三、有機錫化合物的環境效應………………………………………6
1.有機錫化合物進入環境的傳輸途徑………………………….6
2.有機錫化合物的分解及生物甲基化………………………….6
3.有機錫化合物的吸附行為…………………………………….8
四、有機錫化合物的分析方法………………………………………10
1.將欲分析物自樣品基質(matrix)分離…………………………10
2.形成衍生物…………………………………………………….12
3.濃縮…………………………………………………………….14
4.清除(cleanup)步驟……………………………………………..14
5.層析分離及偵測……………………………………………….14
五、研究目的…………………………………………………………16
貳、實驗材料及方法…………………………………………………20
一、藥品及溶液製備…………………………………………………20
1.藥品…………………………………………………………….20
2.試劑水………………………………………………………….20
3.氯化有機錫貯備溶液的配製………………………………….21
4.四乙基硼化鈉溶液的配製…………………………………….21
5.醋酸—醋酸鈉緩衝溶液之配製……………………………….21
二、儀器與設備………………………………………………………21
1.吹氣捕捉濃縮裝置…………………………………………….21
2.氣相層析儀—脈衝火焰光度偵測器(GC—PFPD)…………….24
三、實驗步驟…………………………………………………………29
1.實驗預備工作………………………………………………….29
2.標準溶液的配製……………………………………………….34
3.分析操作步驟………………………………………………….34
四、四乙基硼化鈉溶液濃度的效應…………………………………40
五、吹氣流速的效應…………………………………………………40
六、吹氣時間的效應…………………………………………………42
七、脫附時間的效應…………………………………………………42
八、緩衝溶液pH值的效應………………………………………….42
九、脈衝火焰光度偵測器氫氣流速的效應…………………………42
十、脈衝火焰光度偵測器光電倍增管電壓的效應…………………43
十一、標準檢量線製作………………………………………………43
十二、分析方法偵測極限的測試……………………………………43
十三、環境樣品分析…………………………………………………44
十四、樣品回收率測試………………………………………………44
參、結果………………………………………………………………45
一、分析方法層析圖…………………………………………………45
二、實驗因子對有機錫分析訊號的效應……………………………45
1.四乙基硼化鈉溶液濃度的效應……………………………….45
2.吹氣流速的效應……………………………………………….49
3.吹氣時間的效應……………………………………………….49
4.脫附時間的效應……………………………………………….49
5.緩衝溶液pH值的效應………………………………………..52
6.脈衝火焰光度偵測器氫氣流速的效應……………………….52
7.光電倍增管電壓(PMT)的效應………………………………..56
三、最佳實驗條件……………………………………………………58
四、檢量線線性範圍…………………………………………………58
五、分析方法偵測極限………………………………………………61
六、環境樣品分析……………………………………………………61
七、回收率……………………………………………………………61
肆、討論…………………………………………………….………...68
一、衍生化試劑………………………………………………………68
二、吹氣捕捉濃縮裝置………………………………………………69
二、緩衝溶液…………………………………………………………69
三、脈衝火焰光度偵測器……………………………………………72
1.偵測器的溫度………………………………………………….72
2.閘門延後(gate delay)的時間…………………………………..72
3.燃料氣體的組成……………………………………………….74
4.光電倍增管電壓……………………………………………….74
五、與其他分析方法靈敏度之比較…………………………………75
六、環境樣品測量……………………………………………………77
伍、結論………………………………………………………………80
陸、參考資料…………………………………………………………81
圖 目 錄
頁次
圖一、有機錫化合物進入環境的傳輸途徑…………………………7
圖二、三丁基錫化合物及三苯基錫化合物分解流程圖……………9
圖三、水樣、底泥及生物樣品中有機錫化合物的分析方法………11
圖四、吹氣捕捉濃縮裝置操作程序簡圖……………………………22
圖五、脈衝火焰光度偵測器構造圖…………………………………25
圖六、脈衝火焰光度偵測器形成脈衝火焰程序圖…………………26
圖七、脈衝火焰光度偵測器之氣體進出口示意圖…………………28
圖八、碳的發射圖譜…………………………………………………30
圖九、碳氫化合物的發射時間圖……………………………………31
圖十、錫的發射圖譜…………………………………………………32
圖十一、錫的發射時間圖……………………………………………33
圖十二、吹氣捕捉濃縮裝置吹氣步驟之氣流示意圖………………37
圖十三、吹氣捕捉濃縮裝置乾燥吹氣步驟之氣流示意圖…………38
圖十四、吹氣捕捉濃縮裝置脫附步驟之氣流示意圖………………39
圖十五、吹氣捕捉濃縮裝置清潔步驟之氣流示意圖………………41
圖十六、工作溶液層析圖譜…………………………………………46
圖十七、四乙基硼化鈉層析圖譜……………………………………47
圖十八、四乙基硼化鈉溶液濃度對有機錫分析訊號強度的效應…48
圖十九、吹氣流速對有機錫分析訊號強度的效應…………………50
圖二十、吹氣時間對有機錫分析訊號強度的效應…………………51
圖二十一、脫附時間對有機錫分析訊號強度的效應………………53
圖二十二、緩衝溶液pH值對有機錫分析訊號強度的效應……….54
圖二十三、脈衝火焰光度偵測器氫氣流速對有機錫分析訊號強度的
效應……………………………………………………………………55
圖二十四、光電倍增管電壓對有機錫分析訊號雜訊比(S/N)的效應
…………………………………………………………………………57
圖二十五、DBT檢量線……………………………………………...59
圖二十六、TBT檢量線……………………………………………...60
圖二十七、環境樣品分析取樣點位置………………………………63
圖二十八、高雄港水樣實測結果之柱狀圖…………………………65
圖二十九、三丁基錫化合物進行乙基化衍生反應的可能機制……71
圖三十、脈衝火焰光度偵測器溫度對偵測訊號的影響……………73
表 目 錄
頁次
表一、有機錫化合物的主要用途……………………………………4
表二、吹氣捕捉濃縮裝置之操作條件設定…………………………35
表三、有機錫化合物之方法偵測極限………………………………62
表四、高雄港水樣實測結果…………………………………………64
表五、有機錫化合物之回收率………………………………………67
表六、水樣中有機錫化合物分析方法之比較………………………76
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