臺灣博碩士論文加值系統

超音波泥漿取樣法（Ultrasonic slurry sampling，USS）結合了液態取樣法及固體取樣法的優點，像水溶液一樣可以簡單的改變泥漿濃度，此法常被應用在電熱式揮發裝置（Electrothermal vaporization，ETV），此裝置是屬於乾進樣系統，相較於傳統氣動式霧化器而言，可降低氧化物造成的光譜干擾以及有較好的傳輸效率。此兩種裝置目前已經廣泛的結合感耦合電漿質譜儀（Inductively coupled plasma mass spectrometry，ICP-MS）進行各式樣品中的微量元素分析。研究使用 USS-ETV-ICP-MS，可以直接對固體樣品進行偵測，有別於傳統固體樣品需經過複雜且耗時的前處理步驟以及可以降低在前處理過程中可能導入的汙染或易揮發分析物的損失，造成定量上的不準確。
研究分為兩部分，第一部分研究是利用泥漿取樣法結合電熱式揮發感應耦合電漿質譜儀於海藻中微量稀土元素分析之應用。本研究主要針對稀土元素中釹、釓、鏑及鎦進行偵測分析；研究中將對於修飾劑、泥漿樣品的製備及儀器設定等參數條件進行探討。由實驗結果得知，利用 2.0% Thioacetamide（TAC）以及 0.3% 8-Hydroxyquinoline-5-sulfonic acid（8-HQ-5-SA）作為混合修飾劑，能夠有效地降低分析物揮發溫度，提升分析物的訊號；泥漿樣品配製則選擇以 1.0% m/v 泥漿樣品濃度作為最適化條件，因泥漿樣品濃度太低，分析物產生的訊號較小，容易導致定量上的不準確性，而且泥漿樣品濃度太高將會導致非常大的基質壓抑效應，易使樣品揮發不完全。在儀器參數部分，探討裂解溫度及揮發溫度，最適化條件分別為 350oC 及 2700oC，可得到較佳的分析物訊號，並在之後探討是否會有干擾物造成光譜干擾。最後對桃葉標準參考樣品（NIST SRM-1547）及四種市售海藻樣品進行定量分析。此方法對釹、釓、鏑及鎦的方法偵測極限分別可達 0.3、0.6、0.02 及 0.02 ng g-1。
第二部分研究為低溫揮發法結合電熱式揮發感應耦合電漿質譜儀於藥用活性碳中微量元素分析之應用。本研究使用低溫揮發法，期望能利用此法在低溫時就能夠將分析物（鎘、銻、碲、汞、鉈及鉛）完全揮發進入 ICP-MS 進行偵測，最後在由清除步驟將較難揮發基質去除。研究中分別對修飾劑、泥漿樣品配製以及儀器設定條件等便因進行探討，選用的修飾劑為 Disodium ethylenediamine tetraacetic acid（EDTA），EDTA 能夠有效地將需要高溫揮發的分析物轉變成較低溫度便可進行揮發，以 1.0% m/v EDTA作為最適化濃度。泥漿樣品配製則選擇以 1.0% m/v 泥漿樣品濃度作為最適化條件。在儀器參數部分，探討裂解溫度及揮發溫度，最適化條件分別為 150oC 及 1000oC，可得到較佳的分析物訊號，並在之後探討是否會有干擾物造成光譜干擾。最適化條件探討完後，對本研究低溫揮發法與傳統高溫揮發方法比較，分析物訊號可提升 1.4-3.1 倍之多。最後再以煤灰標準參考樣品（NIST SRM-1633b）以及市售藥用活性碳樣品，分別使用標準添加法及同位素稀釋法作定量分析，來驗證方法之可行性。此方法對鎘、銻、碲、汞、鉈及鉛的方法偵測極限分別可達 0.2、0.1、0.1、0.1、0.02 以及 0.6 ng g-1。

The majority of analysis by ICP-MS are carried out on solutions using a conventional pneumatic nebulizer. However, the type of analytical tasks that can be solved by ICP-MS can be extended using a number of other sample introduction techniques that can be easily adapted to ICP-MS. Electrothermal vaporization (ETV) is one of the sample introduction techniques, that is currently employed in ICP-MS. This alternative technique to solution nebulization presents several advantages, including improved sensitivity, small sample size requirements and the capability of solid analysis. Perhaps the most notable benefit of ETV-ICP-MS is the possibility of performing direct solids analysis.
Ultrasonic slurry sampling is one of the methods for direct solid sample introduction, that has been successfully used in ETAAS. More recently, this approach has been extended to ETV-ICP-MS. Compared to traditional sample preparation methods such as acid digestion and dry pyrolysis, slurry sampling offers several benefits including reduced sample preparation time, reduced possibility of sample contamination, and decreased possibility of analyte loss before analysis. Furthermore, slurry sampling combines the benefits of solid and liquid sampling and permits the use of conventional liquid sample handling apparatus such as an autosampler.
First reaserch, ultrasonic slurry sampling electrothermal vaporization isotope dilution inductively coupled plasma mass spectrometry USS-ETV-ICP-MS. has been applied to the determination of Nd, Gd, Dy and Lu in seaweed samples. Thioacetamide (TAC) and 8-hydroxyquinoline-5-sulfonic acid (8-HQ-5-SA) was used as the modifier. Since the sensitivities of the elements studied in seaweed slurry and aqueous solution were quite different, standard addition method was used for the determination of Nd, Gd, Dy and Lu in these seaweed samples. This method has been applied to the determination of Nd, Gd, Dy and Lu in NIST SRM 1547 peach leaves reference material and four seaweed samples. Analysis results of reference sample NIST SRM 1547 peach leaves agreed satisfactorily with the information values. Detection limits estimated from standard addition curves were 0.3, 0.6, 0.02 and 0.02 ng g-1 for Nd, Gd, Dy and Lu, respectively.
Second research, a low temperature electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) method was developed for the determination of the medicinal activated charcoal, using Ethylenediaminetetraacetic acid (EDTA) as chemical modifier. In this study, a relatively low vaporization temperature was used which separated the analyte from the major matrix components and improved the ion signals significantly. Since the sensitivities of Cd, Sb, Te, Hg, Tl and Pb in various medicinal activated charcoal slurries and aqueous solution were quite different, the standard addition method and isotope dilution method were used for the determination of Cd, Sb, Te, Hg, Tl and Pb in these medicinal activated charcoal samples. This method has been applied to the determination of Cd, Sb, Te, Hg, Tl and Pb in NIST SRM 1633b coal fly ash reference material and four seaweed samples. Analysis results of reference sample NIST SRM 1633b coal fly ash agreed satisfactorily with the certified values. Detection limits estimated from standard addition curves were 0.2, 0.1, 0.1, 0.1, 0.02 and 0.6 ng g-1 for Cd, Sb, Te, Hg, Tl and Pb, respectively.

目錄
謝誌 i
論文提要 ii
目錄 vi
圖表目錄 viii

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海藻中微量稀土元素分析之應用
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 4
貳、實驗部分 7
一、儀器裝置及操作條件 7
二、試劑藥品及溶液的配製 11
參、結果與討論 16
一、修飾劑的選擇 16
二、添加氟化物與鹼對分析物訊號之影響 18
三、裂解溫度及揮發溫度的探討 18
四、稀釋倍數的探討 22
五、界面活性劑對訊號的影響 26
六、酸對分析元素訊號的影響 26
七、光譜（同質量）干擾 26
八、校正曲線 34
九、樣品分析 34
肆、結論 44
伍、參考文獻 45

第二章 低溫揮發法結合電熱式揮發感應耦合電漿質譜儀於藥用活性碳中微量元素分析之應用
壹、前言 49
一、研究背景 49
二、鎘、碲、銻、汞、鉈及鉛之個論 51
三、同位素稀釋法 52
貳、實驗部分 53
一、儀器裝置及操作條件 53
二、試劑藥品及溶液的配製 53
參、結果與討論 62
一、修飾劑的選擇 62
二、界面活性劑對分析物訊號的影響 66
三、酸對分析物訊號的影響 66
四、稀釋倍數的探討 70
五、裂解溫度及揮發溫度的探討 70
六、低溫揮發法與傳統高溫揮發方法比較 74
七、光譜（同質量）干擾 74
八、校正曲線 77
九、定量分析 81
肆、結論 88
伍、參考文獻 89

第一章 文獻
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