超音波泥漿取樣法（USS，Ultrasonic Slurry Sampler）是一種將固體樣品導入電熱式揮發器（ETV，electrothermal Vaporization）的方法，相較於傳統固體樣品需經強酸消化再進行分析，泥漿取樣法的直接取樣分析有簡化樣品前處理的繁雜過程、避免於樣品前處理過程中導入污染物及降低易揮發分析物種在消化時之損失等優點。ETV的樣品輸入裝置具有樣品傳輸效率佳、去除基質易及所需樣品體積少（＜100 μl）等優點，再配合感應偶合電漿質譜儀的高靈敏度、低偵測極限及多元素同時偵測的特性，將有助於固體樣品中微量金屬元素的分析。本研究即利用超音波泥漿取樣法結合電熱式揮發感應偶合電漿質譜儀(USS-ETV-ICP-MS)，直接測定米及塑膠樣品中鉻、銅、鎘、鉛、汞等重金屬的含量，以建立固體樣品的分析方法。
本研究分為兩部分，第一部份係利用USS-ETV-ICP-MS直接測定米樣品中Cr、Cu、Cd、Hg、Pb等元素，第二部份為利用USS-ETV-ICP-MS直接測定塑膠樣品中Cr、Cd及Pb等元素，以建立固體樣品的分析方法。
本研究中並藉由DRC( Dynamic Reaction Cell )系統結合ICP-MS，以降低ICP-MS分析上的光譜干擾，其中進行Cu、Cr及Cd的分析時，會受到基質中C、Cl、Ti、Mo等成分形成的多原子離子干擾，如40Ar12C+、35Cl16OH+干擾52Cr+、37Cl16O+干擾53Cr+、48TiNH3+干擾65Cu+及96MoNH3+干擾113Cd+等，造成質量重疊，所以在偵測時就會受到影響，而使實驗結果產生誤差。因此本研究將配合DRC系統，以氨氣作為反應氣體，藉著分析物與干擾離子間不同的化學反應，以去除樣品基質所造成的同質量干擾。研究中在進行DRC系統變數的探討時， ETV的升溫程式需花費很長的時間，而超音波霧化器具有去溶劑系統，與ETV的進樣系統同為乾的煙霧質( dry aerosol )，因此我們以超音波霧化器來模擬ETV的進樣方式，進行DRC系統變數的探討，而有效地縮短分析的時間。
本研究將針對ETV操作變數、樣品製備、基質修飾劑及DRC最佳化條件等做一有系統的探討。最後分別使用標準添加法及同位素稀釋法來定量塑膠及米標準參考樣品中分析物之濃度，以避免基質不同所造成的靈敏度差異，並證實本實驗所建立的分析方法在實際應用上的可行性。

Ultrasonic slurry sampling electrothermal vaporization dynamic reaction cellTM inductively coupled plasma mass spectrometry (USS-ETV-DRC-ICP-MS) has been applied to determine Cr, Cu, Cd, Hg and Pb in several rice samples. The influences of instrument operating conditions and slurry preparation on the ion signals were reported. Ascorbic acid was used as the modifier to enhance the ion signals. The background ions at the chromium masses were reduced in intensity significantly by using 0.4 ml min-1 NH3 as reaction cell gas in the dynamic reaction cell (DRC) while a q value of 0.6 was used. Since the sensitivities of Cr, Cu, Cd, Hg and Pb in rice flour slurry and aqueous solution were quite different, standard addition and isotope dilution methods were used for the determination of Cr, Cu, Cd, Hg and Pb in these rice samples. This method has been applied to the determination of Cr, Cu, Cd, Hg and Pb in NIST SRM 1568a rice flour reference material and two rice samples purchased from the market. The analysis results of the reference material agreed with the certified values. The results for the rice samples for which no reference values were available were also found to be in good agreement between isotope dilution method and standard addition method. The method detection limits estimated from standard addition curves were about 0.44, 1.7, 0.4, 0.53 and 0.69 ng g-1 for Cr, Cu, Cd, Hg and Pb, respectively, in original rice flour.Ultrasonic slurry sampling electrothermal vaporization dynamic reaction cellTM inductively coupled plasma mass spectrometry (USS-ETV-DRC-ICP-MS) has been applied to the determination of Cr, Cd and Pb in several plastic samples. The influences of instrument operating conditions and slurry preparation on the ion signals were investigated. NH4NO3 was used as the modifier to enhance the ion signals. The background ions at the chromium masses were reduced in intensity significantly by using NH3 as reaction cell gas in the DRC. Standard addition method and isotope dilution method were used for the determination of Cr, Cd and Pb in these plastic samples. This method was applied to the determination of Cr, Cd and Pb in two polystyrene and a polyvinyl chloride samples. The analysis results were found to be in good agreement between isotope dilution method and standard addition method. Furthermore, we digested these samples and analyzed the digested sample solutions by ultrasonic nebulization DRC ICP-MS. The analysis results were close to the isotope dilution and standard addition results. The precision between sample replicates was better than 3% with USS-ETV-DRC-ICP-MS method. The method detection limits estimated from standard addition curves were about 6.2-9.2, 1.1-1.6 and 8.4-11 ng g-1 for Cr, Cd and Pb, respectively, in original plastic samples.

目 錄
論文摘要………………………………………………Ⅰ
謝誌……………………………………………………Ⅲ
目錄……………………………………………………Ⅳ
圖表目錄………………………………………………Ⅶ

第一章 感應偶合電漿質譜儀簡介……………………1
第一節、前言…………………………………………1
第二節、基本原理……………………………………2
第三節、功能與限制…………………………………7
一、光譜性干擾……………………………… 8
二、非光譜性干擾……………………………………8
第四節、Dynamic Reaction 原理…………………10
第五節、應用………………………………………14
一、同位素測量………………………………14
二、元素分析…………………………………17
第六節、參考資料…………………………………18

第二章 電熱式揮發裝置簡介………………………21
第三章 泥漿取樣法結合電熱式揮發感應偶合電漿質譜儀於米樣品中鉻、銅、鎘、鉛及汞等元素之分析應用…30

第一節、前言………………………………………30
第二節、鉻、銅、鎘、汞及鉛之個論……………33
第三節、實驗部份…………………………………37
一、儀器裝置及操作條件……………………37
二、試劑藥品及溶液的配製…………………43
第四節、稻米樣品泥漿的製備……………………46
第五節、結果與討論………………………………51
一、含水量的影響…………………………………51
二、修飾劑的選擇…………………………………51
三、酸及其他試劑對分析物訊號的影響…………53
四、泥漿製備之變數對分析物訊號的影響………59
五、DRC系統之最佳化…………………………… 64
六、熱解溫度及揮發溫度的選擇…………………67
七、樣品定量分析…………………………………70
第六節、結 論…………………………………… 74
第七節、參 考 資 料…………………………… 75
第四章 泥漿取樣法結合電熱式揮發感應偶合電漿質譜儀於塑膠樣品中鉻、鎘及鉛元素之分析應用………79

第一節、前 言………………………………80
第二節、實驗部份…………………………………81
一、儀器裝置及操作條件…………………… 81
二、試劑藥品及溶液的配製………………… 84
第三節、土壤樣品泥漿製備………………………89
第四節、結果與討論………………………………91
一、修飾劑的選擇…………………………………91
二、熱解溫度及揮發溫度的選擇…………………97
三、泥漿製備之變數對分析物訊號的影響………100
四、DRC系統之最佳化……………………………103
五、熱解溫度及揮發溫度的選擇…………………103
六、樣品定量分析…………………………………105
第六節、結 論……………………………………110
第七節、參 考 資 料……………………………111

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