臺灣博碩士論文加值系統

超音波泥漿取樣法（Ultrasonic slurry sampling，USS）是一種將固體樣品以泥漿溶液方式導入乾進樣系統－電熱式揮發（Electrothermal vaporization，ETV）裝置的方法，此直接取樣技術不僅省去繁瑣的樣品前處理，大幅降低因導入汙染物或易揮發之分析物於處理過程中損失等問題，造成定量上的不準確。其配合 ETV 作為樣品輸入裝置，相較於傳統氣動式霧化器而言，能有效地減輕氧化物與氫氧化物造成的光譜干擾，具有較佳的傳輸效率及靈敏度，此外，所需的樣品量少，可避免因樣品量不足造成偵測上的限制。目前已結合感應耦合電漿質譜儀（Inductively coupled plasma mass spectrometry，ICP-MS）進行各式樣品中之微量元素分析。
第一篇研究為泥漿取樣法結合電熱式揮發感應耦合電漿質譜儀於含鈦防曬化粧品中多元素分析之應用。本篇研究中將以低溫揮發方式，藉由分析物（銅、砷、鎘、銻、汞、鉛及鉍）與鈦基質之不同揮發行為，在較低溫度時將待測分析物與基質分離並揮發進入 ICP-MS 中進行偵測。研究中對修飾劑、泥漿樣品的配製、儀器設定條件及光譜干擾等因素進行探討。由實驗結果發現以 0.5% m/v Thioacetamide（TAC）及 0.2% v/v HNO3作為修飾劑有助於改變分析物的揮發行為，提升分析物訊號，並添加 0.1% m/v Triton X-100 進行樣品均勻化。泥漿樣品的配製則選擇 1.0% m/v的濃度，並將揮發溫度設定為 1500oC 時，能有效減輕鈦基質造成的光譜干擾與非光譜干擾，並於研究中探討是否會有干擾物造成光譜干擾。最後對標準參考樣品 GBW09305 和市售含鈦防曬化粧品，分別使用標準添加法與同位素稀釋法作定量分析，驗證此方法的可行性，同時比較消化樣品後以氣動式霧化器進行定量的結果。此方法對於銅、砷、鎘、銻、汞、鉛及鉍元素之方法偵測極限分別為 0.8、0.4、0.2、0.4、0.8、0.5、0.1 ng g-1。
第二篇研究為電熱式揮發感應耦合電漿質譜儀於蜂蜜中鉻、鎘、汞及鉛元素分析之應用。研究中將對動態反應室（Dynamic reaction cell，DRC）系統的條件、修飾劑、樣品的製備、儀器設定等參數進行探討。在 DRC 系統選擇以氧氣作為反應氣體來減輕樣品基質或輸送氣體造成的光譜干擾。此實驗中選擇以0.5% m/v Ascorbic acid 作為修飾劑，並添加 0.6% v/v HNO3減輕碳基質沉積，提升分析物訊號。樣品的配製則選擇 2.0% m/v的濃度作為最適化條件。儀器參數部分則選用 150oC 及 2100oC 作為裂解溫度與揮發溫度，並於研究中探討是否會有干擾物造成光譜干擾。於各分析條件最適化後，將此系統應用於市售蜂蜜的定量分析，由於蜂蜜並無標準參考樣品，實驗中將分別使用標準添加法與同位素稀釋法作定量分析，來驗證方法可行性，並同時消化蜂蜜樣品以氣動式霧化器進行定量並相互比較結果。此方法對於鉻、鎘、汞及鉛元素的方法偵測極限分別為 0.4、0.1、0.6、0.5 ng g-1。

In this reaserch, the use of ultrasonic slurry sampling-electrothermal vaporization- inductively coupled plasma mass spectrometry (USS-ETV-ICP-MS) could be very interesting, as it has proven itself to be: (i) a reliable technique, (ii) better detection power over ETAAS method, (iii) practically sample pretreatment-free, (iv) a multi-elemental capability and (v) small sample volume capability.
The first reaserch, the determination of Cu, As, Cd, Sb, Hg, Pb and Bi in titanium based sunscreens by USS-ETV-ICP-MS was described. Thioacetamide (TAC) was used as the modifier and the influences of instrument operating conditions and slurry preparation on the ion signals were studied. A relatively low vaporization temperature of 1500oC was used, which separated the analyte from the major matrix component, titanium, which improved ion signals. The method has been applied to determine Cu, As, Cd, Sb, Hg, Pb and Bi in GBW09305 Cosmetic (Cream), a reference material and three brands of titanium based sunscreens using isotope dilution and standard addition calibration methods. The concentrations are in good agreement between different calibration methods. The As and Pb analysis results of the reference material agreed with the certified values. The method detection limit estimated from standard addition curves was 0.8, 0.4, 0.2, 0.4, 0.8, 0.5 and 0.1 ng g-1 for Cu, As, Cd, Sb, Hg, Pb and Bi, respectively, in original titanium based sunscreens.
The second reaserch, electrothermal vaporization-dynamic reaction cell-inductively coupled plasma mass spectrometry (ETV-DRC-ICP-MS) has been applied to determine Cr, Cd, Hg and Pb in honey samples. The influences of instrument operating conditions and sample solution preparation on the ion signals were reported. Ascorbic acid was used as a modifier to enhance the ion signals. The background ions at the chromium masses were reduced in intensity significantly by using 1.0 ml min−1 O2 as reaction cell gas in the DRC while a q value of 0.6 was used. Standard addition and isotope dilution methods have been applied to the determination of Cr, Cd, Hg and Pb in four honey samples purchased from the market. The determined values of Cr, Cd, Hg and Pb for the honey samples were also found to be in good agreement between the isotope dilution and standard addition methods. The limits of detection (LOD) from the standard addition curves were about 0.4, 0.1, 0.6 and 0.5 ng g−1 for Cr, Cd, Hg and Pb, respectively.

論文審定書 i
謝誌 ii
中文摘要 iii
英文摘要 v
目錄 vii
圖目錄 ix
表目錄 xi

第一章 泥漿取樣法結合電熱式揮發感應耦合電漿質譜儀於含鈦防曬化粧品中多元素分析之應用
壹、 前言 1
一、 研究背景 1
二、 超音波泥漿取樣法結合電熱式揮發樣品輸入系統簡介 3
三、 銅、砷、鎘、銻、汞、鉛及鉍之個論 6
四、 同位素稀釋法 8
貳、 實驗部分 9
一、 儀器裝置及操作條件 9
二、 試劑藥品及溶液的配製 13
參、 結果與討論 21
一、 修飾劑的選擇 21
二、 界面活性劑對分析物訊號的影響 22
三、 酸對分析物訊號的影響 26
四、 樣品稀釋倍數的探討 26
五、 裂解溫度及揮發溫度的探討 29
六、 光譜（同質量）干擾 29
七、 校正曲線 38
八、 定量分析 38
肆、 結論 46
伍、 參考文獻 47

第二章 電熱式揮發感應耦合電漿質譜儀於蜂蜜中鉻、鎘、汞及鉛元素分析之應用
壹、 前言 53
一、 研究背景 53
二、 動態反應室 55
三、 鉻、鎘、汞及鉛之個論 56
貳、 實驗部分 57
一、 儀器裝置及操作條件 57
二、 試劑藥品及溶液的配製 58
參、 結果與討論 66
一、 ETV-ICP-MS系統中修飾劑的選擇 66
二、 DRC系統之最適化 69
三、 蜂蜜樣品溶液中酸與 H2O2 濃度對分析物訊號的影響 73
四、 蜂蜜樣品稀釋倍數影響的探討 78
五、 電熱式揮發系統裂解溫度及揮發溫度的探討 81
六、 光譜（同質量）干擾 81
七、 校正曲線 86
八、 定量分析 89
肆、 結論 92
伍、 參考文獻 93

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