化學蒸氣生成法最早在1973年由 Braman 等人所發展出的樣品輸入技術，其利用分析物於酸性環境下與還原試劑反應形成氫化物，而氫化物之熔點與沸點相較於分析物下降許多，因此產物會以氣態的形式混在混合液中，再藉由氣液分離裝置將氫化物從液體分離並送入偵測器中。由於氫化物為氣態，相對於傳統氣動式霧化器可以得到較高之樣品傳送效率 (Sample transport efficiency) ，增加訊號之強度，另外使用額外的氣液分離裝置 (Gas-liquid separator，GLS) 有將基質分離之優點，能降低光譜及非光譜性干擾。
第一部分研究利用泥漿進樣法對食品粉末中的鎘、銻及汞做萃取，並以流動注入化學蒸氣生成系統結合感應耦合電漿質譜儀 (FIA-CVG-ICP-MS) 做偵測。實驗中為求得最大訊號，依序對CVG系統中增益試劑thiourea濃度、Co(II)濃度、HCl濃度、還原試劑NaBH4濃度、反應試劑流速、混合線圈體積做最適化探討。另外在CVG系統中使用氣液分離裝置幫助分析物從基質分離，避免鎘及銻之光譜干擾。實驗中比較水溶液校正法 (External calibration) 及標準添加法 (Standard addition) 之斜率，證明基質會壓抑分析物之化學蒸氣生成，因此選擇標準添加法進行定量，並搭配同位素稀釋法 (Isotope dilution) 來驗證結果，本方法之鎘、銻及汞方法偵測極限分別為0.1、0.15、0.1 μg kg-1。為了避免不同物種造成化學蒸氣生成效益之差異，導致定量上的偏差，因此比較Sb(III)及Sb(V)和無機汞及甲基汞在經過泥漿製備法後化學蒸氣生成效率之差異，證實泥漿樣品製備法的還原效果。最後再分析米粉標準樣品NIST 1568a、玉米粉、中筋麵粉、米粉、奶粉及巧克力麥芽粉來驗證本方法之準確性及可行性。
第二部分研究利用HPLC分離水樣中的砷物種，並將分離出的砷物種經由CVG系統產生砷的氫化物，最後經由氣動式霧化器將分析物送入ICP-MS做偵測。以氣動式霧化器做為氣液分離裝置具有系統簡單、不需額外裝置且多一道霧化手續有助於氫化物從分析物溶液釋出等優點。實驗中為求得最大訊號，依序對CVG系統中增益試劑L-cysteine濃度、HCl濃度、還原試劑NaBH4濃度、反應試劑流速、混合線圈長度做最適化探討。由於使用氣動式霧化器做為氣液分離裝置，所使用的HCl試劑會對75As產生40Ar35Cl的光譜干擾，因此額外再加開動態反應槽模式 (Dynamic reaction cell，DRC)，並分別探討氧氣及氫氣作為碰撞氣體之效果，以避免40Ar35Cl對75As的干擾，最後選擇氫氣作為本研究之反應氣體。本實驗使用離子層析 (Ion exchange chromatography) 分離As(III)、DMA、MMA、As(V)，沖提方法採用梯度沖提，實驗中為求得適當之分析時間及訊號，將HPLC與CVG系統串連後依序對pH值、鹽類濃度及LC流速作探討。最後以HPLC-CVG-DRC-ICP-MA系統對標準河水參考樣品SLRS-4、標準和海口水參考樣品SLEW-3、台南地區地下水、美術館池水及澄清湖湖水做偵測並驗證本方法之可行性。

Chemical vapor generation (CVG), initially developed by Braman and Foreback in 1973. The analysis react with reduction in acid and produce hydride compounds. Hydride compounds have much Sample transport efficiency than nebulizer, so it is so sensitive that the method can lower limit detection. Using CVG system can separate analysis from matrix by gas-liquid separator and avoid spectra interfere.
First study using slurry sampling as pretreatment, and determination cadmium, antimony and mercury by SS-FIA-CVG-ICP-MS. To get best signal, testing concentration of thiourea, cobalt, HCl and NaBH4. In addition, testing reagent flow rate and volume of mixing coil, too.Then, we compare slope of external calibration and standard addition to ensure effect by matrix on chemical vapor generation. We choose standard addition and isotope dilution as quantitative method. The experimental method detection limits for cadmium, antimony and mercury are in the range of 0.1-0.15 μg kg-1 . To avoid various species of antimony and mercury affect accuracy of quantitative, we compare chemical vapor generation of Sb(III) and Sb(V) as well as Hg(II) and CH3Hg(II). The accuracy of the method is evaluated by analyzing a rice flour certified reference material (NIST 1568a).
Second study is a method employing a vapor generation system and LC combines with inductively coupled plasma mass spectrometry (LC-ICP-MS) is presented for the determination of arsenic species in water sample. To get best signal, testing concentration of thiourea, HCl and NaBH4. In addition, testing reagent flow rate and volume of mixing coil, too. To avoid 40Ar35Cl interferes with 75As, we choose H2 as reaction gas in DRC system to transfer charge from polyatomic ions 40Ar35Cl+ and get accurate quantitative. We use ion exchange chromatography to separate As(III), DMA, MMA, As(V).The effency of the mobile phase, ammonium carbonate, is evaluated for LC separation of As(III), DMA, MMA, As(V). The sensitivity, detection limits of LC-ICP-MS with a vapor generation is better than LC-ICP-MS with pneumatic nebulization. To get best signal by LC-CVG-ICP-MS, testing pH, concentration of salt and flow rate of LC. The accuracy of the method is evaluated by analyzing riverine water certified reference material (SLRS-4) and estuarine water certified reference material (SLEW-3).

目錄
論文摘要 i
目錄 v
圖表目錄 viii

第一章 流動注入化學蒸氣生成結合感應耦合電漿質譜儀於粉末食品中微量鎘、銻及汞分析之運用
壹、前言 1
一、研究背景 1
二、流動注入分析法 4
三、化學蒸氣生成法 7
四、同位素稀釋法 8
貳、實驗部分
一、儀器裝置 9
二、試劑藥品及溶液配製 10
參、實驗過程
一、化學蒸氣生成系統最佳化條件探討 16
二、ICP-MS系統操作條件之探討 18
三、分析訊號之再現性 19
四、樣品稀釋倍數探討 19
五、光譜干擾探討 19
六、校正曲線及偵測極限估計 20
七、食品粉末樣品前處理及分析 20
肆、結果與討論
一、化學蒸氣生成系統最佳化條件探討 21
二、ICP-MS系統操作條件之探討 33
三、分析訊號之再現性 33
四、樣品稀釋倍數探討 38
五、光譜干擾探討 38
六、校正曲線及偵測極限估計 41
七、食品粉末樣品前處理及分析 44
伍、結論 53
陸、參考文獻 54

第二章 液相層析結合化學蒸氣生成感應耦合電漿質譜儀於水樣中砷物種之分析
壹、前言 59
一、研究背景 59
二、動態反應槽系統 61
貳、實驗部分
一、儀器裝置 62
二、試劑藥品與溶液配製 63
參、實驗過程
一、化學蒸氣生成系統條件最適化之探討 66
二、ICP-MS系統操作條件之探討 67
三、液相層析條件最適化探討 68
四、DRC-ICP-MS系統最適化探討 69
五、分析訊號之再現性 69
六、校正曲線與偵測極限估計 70
七、真實樣品分析 70
肆、結果與討論
一、化學蒸氣生成系統條件最適化之探討 72
二、ICP-MS系統操作條件之探討 79
三、液相層析條件最適化探討 83
四、DRC-ICP-MS系統最適化探討 88
五、分析訊號之再現性 96
六、校正曲線與偵測極限估計 96
七、真實樣品分析 96
伍、結論 109
陸、參考文獻 110

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