感應耦合電漿質譜儀( Inductively Coupled Plasma Mass Spectrometry，ICP-MS )結合了ICP原子化及游離化效率高的特性，以及質譜儀的高靈敏度和測定同位素比的能力，使ICP-MS成為一種極佳的微量多元素分析技術，並具有偵測極限低及線性範圍廣等優點，目前已廣泛地被應用在層析分離法之偵測器。
本研究第一部份是利用毛細管電泳結合動態反應管感應耦合電漿質譜儀於砷及硒物種分析之應用。研究中使用內徑75 μm、長60 cm之毛細管，以含有1 mmol L-1 SDS ( Sodium dodecyl sulphate )之25 mmol L-1 CAPS ( 3-Cyclohexylamino-1-propanesulfonic acid ) pH 9.6作為分離電解質，在+24 kV的分離電壓下，於8分鐘內可有效分離Arsenobetaine (AsB)、Dimethylarsinic acid (DMA)、Monomethylarsonic acid (MMA)、Arsenite [As(III)]、Arsenate [As(V)]、Selenomethionine (SeMet)、Se-Methylselenocysteine (MeSeCys)、Selenocystine (SeCys2)、Selenite [Se(IV)]及Selenate [Se(VI)]等十個物種。由於感應耦合電漿質譜儀在偵測78Se+、80Se+時會遭遇到38Ar40Ar+、40Ar40Ar+的同質量多原子離子干擾，因此本研究藉由通有甲烷(CH4)之動態反應管系統來降低此干擾，而砷則可於背景較低的m/z 89偵測75As12CH2+訊號。各物種滯留時間及波峰訊號(波峰面積)的再現性均優於7%，其校正曲線相關係數除了As(III)及Se(VI)外，其餘物種均優於0.993；砷物種的偵測極限在0.6-2.0 ng mL-1之間，而硒物種的偵測極限在0.6-0.8 ng mL-1之間。最後以建立的系統應用於美術館池水樣品之定量分析，各物種的回收率介於97-108%之間。
本研究第二部分是利用液相層析結合感應耦合電漿質譜儀於鉈物種分析之應用。由於Tl(III)在自然環境中相當不穩定，容易被一般還原試劑還原而改變其氧化態，藉由在標準樣品溶液中添加DTPA ( Diethylenetriamine pentaacetic acid )來穩定Tl(III)。研究中使用C8逆相層析管柱欲分離Tl(I)和Tl(III)兩物種，以5.0 mM TBAP ( Tetra-n- butylammonium Phosphate ) 離子對試劑、4.0 mM DTPA、2% (v/v) MeOH作為動相( pH 6.0)，Tl(I)和Tl(III)可於2分鐘內有效分離，所得各物種滯留時間及波峰訊號的再現性皆優於2%，線性相關係數均呈現1，偵測極限可達0.003 ng mL-1。最後，將所建立的方法應用於中山大學後山龍眼樹及芒果樹葉片及土壤標準樣品( NIST SRM 2711 Montana Soil )中鉈物種之定量分析。

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目 錄
論文提要 ..................................................................................................... I
謝 誌 ........................................................................................................ IV
目 錄 ........................................................................................................ V
圖 目 錄 ................................................................................................ VIII
表 目 錄 .................................................................................................. XI
第一章 毛細管電泳結合感應耦合電漿質譜儀於砷及硒物種分析之應
用
壹、 前言 ............................................................................................... 1
貳、 動態反應管基本原理 ................................................................... 5
參、 實驗部分 ..................................................................................... 10
一、儀器裝置與設備 ........................................................................ 10
二、藥品和溶液的配製 .................................................................... 13
三、毛細管電泳之分析 .................................................................... 18
四、DRC 系統之最適化 .................................................................. 20
五、校正曲線、再現性與偵測極限的估計 ................................... 20
六、樣品分析 .................................................................................... 21
肆、 結果與討論 ................................................................................. 24
一、 CE 分離條件最適化的探討 ................................................ 24

二、 DRC 系統操作條件之最適化 ............................................ 35
三、 砷及硒物種的分離 .............................................................. 43
四、 重複性、檢量線性與偵測極限 .......................................... 45
五、 真實樣品的分析 .................................................................. 49
伍、 結論 ............................................................................................. 56
陸、 參考文獻 ..................................................................................... 57
第二章 液相層析結合感應耦合電漿質譜儀於鉈物種分析之應用
壹、 前言 ............................................................................................. 63
貳、 實驗部分 ..................................................................................... 66
一、儀器裝置 .................................................................................... 66
二、藥品和溶液的配製 .................................................................... 68
參、 實驗過程 ..................................................................................... 71
一、 液相層析分離條件的最適化 .............................................. 71
二、 再現性 .................................................................................. 72
三、 校正曲線與偵測極限的估計 .............................................. 72
四、 真實樣品分析 ...................................................................... 72
肆、 結果與討論 ................................................................................. 78
一、 液相層析分離條件的探討 .................................................. 78
二、 再現性 .................................................................................. 87

三、 校正曲線與偵測極限的估計 .............................................. 87
四、 真實樣品的分析 .................................................................. 91
伍、 結論 ............................................................................................. 99
陸、 參考文獻 ................................................................................... 100
圖 目 錄
第一章 毛細管電泳結合感應耦合電漿質譜儀於砷及硒物種分析之應
用
圖1-1 DRC-ICP-MS 儀器示意圖 ............................................................. 9
圖1-2 商業化CEI-100 介面 .................................................................. 12
圖1-3 十字型轉接頭、低流量霧化器與噴霧室 .................................. 12
圖1-4 魚肝標準樣品隔水加熱萃取的流程圖 ...................................... 23
圖1-5 分離電解質之pH 值對電泳分離的影響 ................................... 26
圖1-6 電解質濃度與Zeta potnetial 的關係 .......................................... 27
圖1-7 分離電解質濃度對電泳分離的影響 .......................................... 28
圖1-8 添加介面活性劑於分離電解質中對電泳分離之影響 .............. 30
圖1-9 添加介面活性劑之分離電解質濃度對電泳分離的影響 .......... 31
圖1-10 分離電壓對電泳分離的影響 .................................................... 33
圖1-11 注射時間對電泳分離的影響 .................................................... 34
圖1-12 以CH4 為反應氣體，固定q 值為0.5，改變氣體流速對砷及
硒訊號的影響..........................................................................................36
圖1-13 以CH4 為反應氣體，固定q 值為0.5，改變氣體流速對預估
偵測極限(EDL)的影響 ............................................................................ 37
圖1-14 以CH4 為反應氣體，設定氣體流速為0.9 mL min-1，改變q
值對砷及硒訊號的影響..........................................................................39

圖1-15 以CH4 為反應氣體，固定氣體流速為0.9 mL min-1，改變q
值對分析物訊號與背景訊號比(Signal / Background)的影響 ............... 40
圖1-16 以CH4 為反應氣體，固定氣體流速為0.9 mL min-1，改變q
值對預估偵測極限(EDL)的影響 ............................................................ 41
圖1-17 分別在(a)標準模式及(b)DRC 模式下分析物的電泳分離圖 . 44
圖1-18 魚肝標準參考樣品(NRCC DLOT-3)的電泳分離圖 ................ 52
圖1-19 美術館池水樣品的電泳分離圖 ................................................ 54
第二章 液相層析結合感應耦合電漿質譜儀於鉈物種分析之應用
圖2-1 HPLC-ICP-MS 之系統圖 ............................................................. 67
圖2-2 TBAP 及DTPA 之結構式 ............................................................ 69
圖2-3 實驗流程 ...................................................................................... 75
圖2-4 植物樹葉樣品密閉式微波萃取的流程圖 .................................. 76
圖2-5 土壤標準樣品隔水加熱萃取的流程圖 ...................................... 77
圖2-6 沖提液中TBAP 濃度對層析分離的影響 .................................. 79
圖2-7 沖提液中DTPA 濃度對層析分離的影響 .................................. 81
圖2-8 沖提液中甲醇濃度對層析分離的影響 ...................................... 82
圖2-9 沖提液之pH 值對層析分離的影響 ............................................ 84
圖2-10 沖提液流速對層析分離的影響 ................................................ 85
圖2-11 龍眼樹葉樣品萃取後所得鉈物種之層析圖 ............................ 93

圖2-12 芒果樹葉樣品萃取後所得鉈物種之層析圖 ............................ 94
圖2-13 Montana Soil 萃取後所得鉈物種之層析圖 .............................97
表 目 錄
第一章 毛細管電泳結合感應耦合電漿質譜儀於砷及硒物種分析之應
用
表1-1 砷及硒物種之化學式及解離常數pKa 值 ................................. 14
表1-2 CE-DRC-ICP-MS 實驗操作最適化條件 ..................................... 42
表1-3 砷和硒物種在標準模式及DRC 模式下的校正曲線及偵測極限
................................................................................................................... 46
表1-4 CE-ICP-MS 與其他系統偵測極限比較（砷物種） .................. 47
表1-5 CE-ICP-MS 與其他系統偵測極限比較（硒物種） .................. 48
表1-6 砷和硒物種的遷移時間及訊號的再現性 .................................. 51
表1-7 以CE-DRC-ICP-MS 測定水樣中的砷及硒物種 ...................... 55
第二章 液相層析結合感應耦合電漿質譜儀於鉈物種分析之應用
表2-1 分析物在HPLC-ICP-MS 系統之最適化條件 ............................ 86
表2-2 鉈物種的滯留時間及分析訊號之再現性 .................................. 88
表2-3 鉈物種之校正曲線及偵測極限 .................................................. 89
表2-4 HPLC-ICP-MS 與其他系統偵測極限比較 ................................. 90
表2-5 以HPLC-ICP-MS 測定植物樹葉樣品中鉈物種之含量及回收率
................................................................................................................... 95
表2-6 以HPLC-ICP-MS 測定土壤標準樣品( NIST SRM 2711 Montana
Soil )中鉈物種之含量及回收率 .............................................................. 98

第一章 毛細管電泳結合感應耦合電漿質譜儀於砷及硒物種分析之應用
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第二章 液相層析結合感應耦合電漿質譜儀於鉈物種分析之應用
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