稻米為亞洲人重要的主食，因此，相較於其他農產品，稻米早已成為亞洲人砷暴露的重要來源之一。一般來說，砷可以許多不同的化學形式存在於環境介質之中，同時透過環境的傳播及人類的活動大量累積在人體之中。根據文獻報導，稻米中存在的砷物種主要是以無機砷(三價砷及五價砷)以及雙甲基砷居多，有鑑於砷的毒性強度與其氧化價態及化學型態息息相關，因此，掌握稻米中砷物種濃度分布資訊，對於確認稻米可被食用的安全性是絕對必要的。為達上述目的，本研究係利用化學蒸氣生成法結合高效能液相層析技術與感應耦合電漿質譜儀，建立一套具有選擇性及高靈敏度的連線分析系統來進行稻米中砷物種之分析測定。有別於過去，本研究所使用的化學蒸氣生成技術係首度使用連二亞硫酸鈉作為還原試劑，透過此一新穎化學試劑的使用，毋須經過額外樣品前處理程序即可有效地將所欲分析之砷物種氣化，並與樣品中可能的干擾物分離。同時，相較於傳統化學蒸氣生成法中所使用的還原試劑(硼氫化鈉、氯化亞錫等)，連二亞硫酸鈉的毒性大幅降低，價格也明顯較低。根據實驗結果顯示，本研究所建立之連線分析系統不僅在稻米中砷物種分析提供了可信的測定結果，亦已符合當今綠色化學對於分析方法必須具備環境友善特性的需求。

Rice is a staple of the diet in Asia and contributes more arsenic (As) to the Asian diet than all other agricultural products. A variety of chemical forms of naturally occurring As can be arisen from natural sources and anthropogenic activities. According to literature report, the main As species that occurs in rice are inorganic As (e.g. As(III) and As(V)) and dimethylarsinic acid (DMA). Because the adverse effects of As is highly dependent on its oxidation state, speciation information for rice As is necessary to ensure that rice can be safely consumed. In this study, we developed a selective and sensitive hyphenated system employing a chemical vapor generation (CVG) system in conjunction with high-performance liquid chromatography (HPLC) separation and inductively coupled plasma-mass spectrometry (ICP-MS) detection for the determination of As species in rice samples. The CVG system innovatively exploited a chemical reagent, sodium dithionite (Na2S2O4), to selectively convert As species into volatile products for separating interest analytes from possible interferences in rice extractant samples. Based on the experimental results, the As species of interest could be efficiently vaporized with the aid of Na2S2O4 without any further treatment. By contrast, the toxicity of the used chemicals in this study is much lower than that of the conventional reduction reagents, such as sodium borohydride (NaBH4) and tin(II) chloride (SnCl2). These satisfactory results demonstrated that our proposed system was not only reliable for the determination of As species in rice samples but also environmental-friendly fulfilling the goals of “Green Chemistry”.

摘要 I
Abstract II
謝誌..............................................................................................................................IV
目錄 VI
圖目錄 IX
表目錄 XI
第一章 前言 1
1.1 稻米中砷物種濃度分析的重要性 1
1.1.1 砷物種的毒性以及代謝機制 3
1.1.2 稻米中砷的來源以及物種分布 7
1.2 砷物種分析技術發展 9
1.3 蒸氣生成法 10
1.3.1 化學蒸氣生成法 (Chemical vapor generation, CVG) 10
1.3.2 光化學蒸氣生成法 (Photochemical vapor generation, photo-CVG) 11
1.3.3 光觸媒輔助蒸氣生成法 (Photo-catalyst assisted vapor generation) 11
1.4 研究目的與方法 13
第二章 儀器分析及原理 14
2.1 高效能液相層析儀 14
陰離子交換層析法 18
逆相層析法 19
2.2 感應耦合電漿質譜儀 20
2.2.1 樣品導入系統 21
2.2.2 感應耦合電漿離子源 23
2.2.3 離子透鏡 (Ion lens) 26
2.2.4 四極柱質量分析器 29
2.2.5 離子偵測 30
第三章 實驗部分 33
3.1 藥品與儀器 33
3.1.1 試劑與材料 33
3.1.2 儀器裝置 34
3.2 化學蒸氣生成法產物鑑定之樣品製備 35
3.3 連線分析系統建立 38
3.4 真實樣品分析 38
3.4.1 樣品處理 38
3.4.2 萃取 38
第四章 結果與討論 42
4.1 連二亞硫酸鈉蒸氣生成技術反應機制之研究 42
4.2 層析分離操作條件最適化探討 50
4.3 化學蒸氣生成法操作條件最適化探討 53
4.3.1 還原試劑濃度最適化 53
4.3.2 pH值最適化 54
4.3.3 還原反應溫度最適化 56
4.3.4 還原反應時間最適化 58
4.4 連線分析系統特性與效能評估 59
4.4.1 連線分析系統特性與分析方法確效 59
4.4.2 真實樣品中砷物種分析 62
4.4.3 方法比較 64
第五章 結論 67
第六章 參考文獻 70
第七章 未來展望 77
附錄–論文口試審查委員意見修正情形一覽 81

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