臺灣博碩士論文加值系統

霧點萃取法( Cloud Point Extraction，CPE )是利用螯合試劑先與分析物結合，再以界面活性劑進行濃縮萃取的方法，此方法可以降低偵測極限並將基質分離，避免環境水樣中高濃度的鹽類基質對分析物造成光譜及非光譜性干擾。化學蒸氣生成法( Chemical Vapor Generation，CVG )是一種廣泛應用在原子光譜及質譜分析的進樣方式，此方法利用氣體生成技術將分析物與溶液中之基質分離，具有增加分析物的樣品傳輸效率、提升靈敏度、降低偵測極限及減輕光譜干擾等優點。本研究將結合蒸氣生成法與感應耦合電漿質譜儀( Inductively coupled plasma mass spectrometry，ICP-MS )對環境水樣中鎘、銻、汞與酒樣中多元素分析之應用。
研究中分為兩部分:第一部份為霧點萃取法結合化學蒸氣生成感應耦合電漿質譜儀偵測環境水樣中之鎘、銻及汞微量元素。實驗中霧點萃取條件，包含萃取溶液pH值、螯合試劑APDC與界面活性劑Triton X-114濃度、萃取時間及溫度等進行探討，以最適化所得界面活性層以流動式注入化學蒸氣生成導入ICP-MS偵測；另外在蒸氣生成系統的最適化探討條件，包含載體溶液中增益試劑thiourea、Co(II)與HCl濃度、還原試劑NaBH4濃度、反應試劑流速及混合線圈長度等對分析物訊號的影響。以CVG做為進樣裝置能有效的將Mo與Zr基質分離，減低氧化物及氫氧化物對Cd與Sb的干擾。實驗中將使用基質匹配檢量線（Matrix-matched calibration）與同位素稀釋法( Isotope dilution )進行定量，鎘、銻及汞的偵測極限分別為2.0、0.6及5.0 ng L-1。最後將分析河水標準參考樣品NRCC SLRS-4及河海口水標準參考樣品NRCC SLEW-2、愛河河水、澄清湖湖水、中山大學自來水及礦泉水樣品來驗證此方法的實用性。
第二部分研究利用蒸氣生成系統及薄膜去溶劑系統分別結合ICP-MS來偵測酒類樣品中微量元素。由於酒樣品以傳統氣動式霧化器直接進樣，需考量高揮發性物質是否造成電漿不穩定或燃燒不完全的碳基質沉積於取樣錐，進而影響分析結果。本實驗以CVG-ICP-MS來偵測酒樣中的微量元素，不須經繁雜的樣品前處理，以流動式注入方式同時偵測酒樣中銻、汞及鉛三種元素，研究中以乙醇為模擬基質，探討CVG-ICP-MS系統條件之最適化，包括樣品和載體溶液中HCl與thiourea、NaBH4及氧化劑K3Fe(CN)6濃度等。在最適化條件下於乙醇基質中添加1.0 μg L-1 銻、汞及鉛元素標準溶液以測定訊號再現性，所測得之分析訊號( n=7 )波峰面積及波峰高度相對標準偏差( RSD )皆小於3.9%以下；另外在Aridus去溶劑裝置尋找系統之最適化，包含霧化氣體流速、掃除氣體氣體流速、氮氣氣體流速、噴霧腔與薄膜溫度。由於樣品基質差異造成標準添加法與水溶液校正曲線法靈敏度不同，因此本實驗蒸氣生成法以標準添加法及同位素稀釋法進行定量，銻、汞及鉛的偵測極限各為1.0、8.0及13 ng L-1。最後，將所開法之兩方法應用於市售啤酒、紅酒、米酒及高粱酒，並將其結果與薄膜去溶劑裝置Aridus-ICP-MS定量比較，進一步驗證此方法之準確性與可行性。

目錄
論文提要 .......................................................................................................................Ⅰ
謝誌 .............................................................................................................................. III
目錄 .............................................................................................................................. IV
圖表目錄 ......................................................................................................................VII

第一章 霧點萃取法結合化學蒸氣生成感應耦合電漿質譜儀於水樣中微量鎘、銻及汞分析之應用
壹、 前言 ........................................................................................................................ 1
一、 研究背景.......................................................................................................... 1
二、 霧點萃取法( Cloud point extraction，CPE)簡介…........................................ 2
三、 化學蒸氣生成( Chemical vapor generation，CVG )簡介............................... 4
四、 同位素稀釋( Isotope dilution，ID )簡介 ....................................................... 5
貳、 實驗部分 ................................................................................................................ 7
一、 儀器裝置 ........................................................................................................ 7
二、 試劑藥品和溶液配製 .................................................................................... 8
参、 實驗過程 .............................................................................................................. 12
一、 霧點萃取各參數之探討 .............................................................................. 12
二、 化學蒸氣生成系統各參數之探討 .............................................................. 17
三、 光譜干擾探討 .............................................................................................. 20
四、 校正曲現及偵測極限估計 .......................................................................... 20
五、 真實樣品之霧點萃取及分析 ...................................................................... 20
肆、 結果與討論 .......................................................................................................... 21
一、 霧點萃取各參數之探討 .............................................................................. 21
二、 化學蒸氣生成系統各參數之探討 .............................................................. 31
三、 光譜干擾探討 .............................................................................................. 44
四、 校正曲線及偵測極限估計 .......................................................................... 50
五、 真實樣品之霧點萃取及分析........................................................................ 50
伍、 結論 ..................................................................................................................... 58
陸、 參考文獻 .............................................................................................................. 59

第二章、化學蒸氣生成技術及薄膜去溶劑系統結合感應耦合電漿質譜儀於酒中微
量元素分析之應用
壹、 前言 ...................................................................................................................... 62
一、 研究背景........................................................................................................ 62
貳、 實驗部分 .............................................................................................................. 63
一、 儀器裝置 ...................................................................................................... 63
二、 去溶劑進樣系統簡介 .................................................................................. 64
三、 試劑藥品和溶液配製 .................................................................................. 65
参、 實驗過程................................................................................................................ 70
一、 化學蒸氣生成系統各參數之探討 .............................................................. 70
二、 化學蒸氣生成校正曲線及偵測極限估計 …………................................ 72
三、 以蒸氣生成法偵測真實樣品之及分析 ...................................................... 73
四、 Aridus 薄膜去溶劑系統各參數之探討 ..................................................... 73
五、 薄膜去溶劑系統之光譜干擾探討及偵測極限估計 .................................. 74
六、 以薄膜去溶劑系統分析真實樣品及結果比較 .......................................... 74
肆、 結果與討論............................................................................................................ 75
一、 化學蒸氣生成系統各參數之探討 .............................................................. 75
二、 化學蒸氣生成校正曲線及偵測極限估計.................................................... 88
三、 以蒸氣生成法偵測真實樣品之及分析 ...................................................... 93
四、 Aridus 薄膜去溶劑系統各參數之探討 ..................................................... 96
五、 薄膜去溶劑系統之光譜干擾探討及偵測極限估計 ................................ 112
六、 以薄膜去溶劑系統分析真實樣品及結果比較 ........................................ 118
伍、 結論 .................................................................................................................... 122
陸、 附錄 ……............................................................................................................ 123
柒、 參考文獻 ............................................................................................................ 125

圖表目錄

第一章 霧點萃取法結合化學蒸氣生成感應耦合電漿質譜儀於水樣中微量鎘、銻
及汞分析之應用

圖1-1、霧點萃取法流程圖 ............................................................................................ 3
圖1-2、不同微胞形式的界面活性劑 ............................................................................ 3
圖1-3、流動注入化學蒸氣生成系統裝置圖 ................................................................ 9
圖1-4、本實驗所使用的試劑(a)APDC與(b)Triton X-114 .......................................... 15
圖1-5、APDC與金屬離子螯合錯合物結構圖 ........................................................... 16
圖1-6、界面活性劑形成微胞萃取之結構示意圖 ...................................................... 16
圖1-7、pH值對各元素萃取效率的影響 ..................................................................... 22
圖1-8、螯合試劑APDC濃度對各元素萃取效率的影響 ........................................... 23
圖1-9、界面活性劑Triton X-114濃度對各元素萃取效率的影響 ............................ 24
圖1-10、微波萃取溫度對各元素萃取效率的影響 .................................................... 26
圖1-11、微波萃取時間對各元素萃取效率的影響 ..................................................... 27
圖1-12、實驗之霧點萃取流程圖 ................................................................................ 30
圖1-13、樣品及載體溶液中thiourea濃度對Cd、Sb及Hg元素(a)、(b)分析物波峰面積訊號及(c)波峰高度S/B的影響 ........................................................... 33
圖1-14、樣品及載體溶液中Co(II)濃度對Cd、Sb及Hg元素(a)、(b)分析物波峰面積訊號及(c)波峰高度S/B的影響 …........……………............................... 34
圖1-15、還原試劑NaBH4濃度對Cd、Sb及Hg元素(a)、(b)分析物波峰面積訊號及(c)波峰高度S/B的影響 …...….……………………............................... 36
圖1-16、載體溶液中HCl濃度對Cd、Sb及Hg元素(a)、(b)分析物波峰面積訊號及(c)波峰高度S/B的影響 …....…..…..……............................................... 37

圖1-17、反應試劑流速對Cd、Sb及Hg元素(a)波峰面積相對訊號(b)波峰高度S/B的影響 .......................................................................................................... 38
圖1-18、CVG-ICP-MS系統中，電漿功率對Cd、Sb及Hg元素(a)波峰面積相對訊號(b)波峰高度S/B的影響 …....................................................................... 40
圖1-19、CVG-ICP-MS系統中，載送氣體流速對Cd、Sb及Hg元素(a)波峰面積相對訊號(b)波峰高度S/B的影響 ……........................................................... 41
圖1-20、CVG-ICP-MS系統中，混合線圈長度對Cd、Sb及Hg元素(a)波峰面積相對訊號(b)波峰高度S/B的影響 ................................................................... 42
圖1-21、比較(a)Cross-flow nebulizer with Scott-type spray chamber氣動式霧化器以及(b)Flow injection chemical vapor generation流動式注入化學蒸氣生成系統，觀察基質中Mo及Zr對Cd、Sb之干擾程度 ....................................... 48
圖1-22、河水標準參考樣品SLRS-4之蒸氣生成訊號圖 ……................................... 56
圖1-23、礦泉水之蒸氣生成訊號圖 …..…..……….................................................... 57


表1-1、鎘、銻及汞同位素之含量比 ............................................................................. 11
表1-2、以霧點萃取法對不同金屬進行霧點萃取 ...................................................... 13
表1-3、以最適化霧點萃取條件Sb(III)、Sb(V)及Sb(III)與Sb(V)的溶液進行霧點萃取之結果 ........................................................................................................ 28
表1-4、以最適化霧點萃取條件對Hg、MeHg及Hg與MeHg的溶液進行霧點萃取之結果 ............................................................................................................ 28
表1-5、添加干擾離子濃度對分析物萃取效率影響 .................................................. 29
表1-6、不同增益試劑對Cd、Sb及Hg訊號之比較 ................................................... 32
表1-7、Cd、Sb與Hg分析訊號之再現性 ………........................................................ 43
表1-8、CVG-ICP-MS最適化條件 ............................................................................... 45
表1-9、不同預濃縮倍數( Preconcentration factor，PCF )對分析訊號影響 ……....... 46
表1-10、各偵測同位素之自然界含量與質量干擾 .................................................... 47
表1-11、標準參考水樣品中Mo、Cd及Sb之含量 ..................................................... 47
表1-12、多原子離子對Cd、Sb訊號及同位素比測量影響 ........................................ 49
表1-13、Cd、Sb及Hg基質匹配校正曲線及偵測極限 .............................................. 51
表1-14、以基質匹配校正曲線法與同位素稀釋法定量標準參考樣品NRCC SLRS-4及SLEW-2 .................................................................................................... 53
表1-15、以霧點萃取法結合CVG-ICP-MS定量礦泉水、中山大學自來水、澄清湖湖水與愛河河水樣品中Cd、Sb及Hg之濃度 ............................................ 54
表1-16、以基質匹配校正曲線法與同位素稀釋法對礦泉水、中山大學自來水、澄清湖湖水與愛河河水樣品進行定量 .......................................................... 55

第二章 化學蒸氣生成技術及薄膜去溶劑系統結合感應耦合電漿質譜儀於酒中微
量元素分析之應用

圖2-1、流動注入化學蒸氣生成系統裝置圖 .............................................................. 66
圖2-2、Aridus薄膜去溶劑進樣系統之構造圖 ........................................................... 67
圖2-3、樣品及載體溶液中thiourea濃度對Sb、Hg及Pb元素(a)分析物波峰面積訊號及 (b) 波峰高度S/B的影響 ....................................................................... 77
圖2-4、氧化劑K3Fe(CN)6濃度對Sb、Hg及Pb元素(a)分析物波峰面積訊號及(b)波峰高度S/B的影響 ....................................................................................... 78
圖2-5、樣品及載體溶液中HCl濃度對Sb、Hg與Pb元素(a)分析物波峰面積訊號及(b)波峰高度之S/B的影響 ........................................................................... 80
圖2-6、NaBH4濃度對Sb、Hg與Pb元素(a)分析物波峰面積訊號及(b)波峰高度之S/B的影響 ........................................................................................................ 81
圖2-7、反應試劑流速對Sb、Hg與Pb元素(a)波峰面積相對訊號(b)波峰高度之S/B的影響 .............................................................................................................. 82
圖2-8、CVG-ICP-MS系統中，儀器電漿功率對Sb、Hg與Pb元素(a)波峰面積相對訊號(b)波峰高度之S/B的影響 ................................................................... 84
圖2-9、CVG-ICP-MS系統中，載送氣體流速對Sb、Hg與Pb元素(a)波峰面積相對訊號(b)波峰高度之S/B的影響 ................................................................... 85
圖2-10(a) (b)、氣液分離中液面高度低與高之訊號圖 .............................................. 89
圖2-11、啤酒樣品以CVG-ICP-MS分析之訊號圖 .................................................... 99
圖2-12、米酒樣品以CVG-ICP-MS分析之訊號圖 .................................................. 100
圖2-13、使用Aridus進樣系統探討噴霧腔溫度對多元素分析訊號的影響 …....... 101
圖2-14、使用Aridus進樣系統探討薄膜溫度對多元素分析訊號的影響 ............... 104
圖2-15、使用Aridus進樣系統探討霧化氣體流速對多元素分析訊號的影響 ....... 106
圖2-16、使用Aridus進樣系統探討掃除氣體流速對多元素分析訊號的影響 ....... 108
圖2-17、使用Aridus進樣系統探討氮氣氣體流速對多元素分析訊號的影響 ....... 110
圖2-18、使用Aridus進樣系統探討電漿功率對多元素分析訊號的影響 ............... 113
圖2-19、使用(a)傳統氣動式霧化器及(b)Aridus進樣系統探討模擬基質對分析物干擾影響 ............................................................................................................ 116


表2-1、銻、汞及鉛同位素之含量比 ............................................................................ 69
表2-2、不同增益試劑對Sb、Hg及Pb訊號之比較 .................................................... 76
表2-3、不同長度之mixing coil對CVG訊號生成的影響 .......................................... 86
表2-4、不同注射體積對分析訊號生成的影響 .......................................................... 87
表2-5、液面高度對分析訊號生成的影響 .................................................................. 89
表2-6、CVG系統Sb、Hg及Pb分析訊號之再現性 .................................................. 90
表2-7、FI-CVG-ICP-MS最適化條件 .......................................................................... 91
表2-8、多原子離子對Sb訊號及同位素比測量影響 ................................................. 92
表2-9、以CVG系統標準添加法與水溶液校正曲線斜率之比較 ............................. 94
表2-10、不同銻物種之蒸氣生成效果比較 ................................................................ 95
表2-11、FI-CVG-ICP-MS以水溶液校正曲線法及同位素稀釋法定量標準參考樣品NRCC SLRS-4和NIST trace element in water 1643b ..................................... 97
表2-12、以FI-CVG-ICP-MS定量米酒、啤酒、高粱酒與紅酒樣品中Sb、Hg及Pb之濃度 ......………………………………………………………………….... 98
表2-13、使用Aridus進樣系統探討噴霧腔溫度對多元素分析訊號比值的影響…. 102
表2-14、使用Aridus進樣系統探討薄膜溫度對多元素分析訊號比值的影響…..... 105
表2-15、使用Aridus進樣系統探討霧化氣體流速對多元素分析訊號比值的影響.107
表2-16、使用Aridus進樣系統探討掃除氣體流速對多元素分析訊號比值的影響. 109
表2-17、使用Aridus進樣系統探討氮氣氣體流速對多元素分析訊號比值的影響. 111
表2-18、使用Aridus進樣系統探討電漿功率對多元素分析訊號比值的影響......... 114
表2-19、使用Aridus進樣系統探討不同乙醇濃度對多元素分析訊號比值的影響. 115
表2-20、Aridus系統分析訊號之再現性 ………....................................................... 117
表2-21、Aridus以水溶液校正曲線法定量標準參考樣品NRCC SLRS-4和NIST trace element in water 1643b .................................................................................... 119
表2-22、Aridus以水溶液校正曲線法定量酒類樣品 ……..........................………. 120
表2-23、酒類樣品中Sb、Hg及Pb之定量結果之比較 .............................………… 121
表2-24、使用Aridus進樣系統探討不同內標準對多元素分析訊號比值的影響.… 124

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