近年來，物種分析的重要性逐漸受到重視，由於元素的化學型態與其毒性程度有極大的關係，對環境的影響也不同。因此相較於總量的測定，不同物種的定量更具代表性、更能提供重要的生物資訊。利用液相層析（Liquid Chromatography，LC）將不同物種分離後，再進入感應耦合電漿質譜儀（Inductively Coupled Plasma Mass Spectrometry，ICP-MS）進行偵測，即可獲得物種間的定量資訊。由於ICP-MS靈敏度高、偵測極限低、線性範圍廣以及同位素分析能力等優點，使得液相層析結合感應耦合電漿質譜儀成為環境或是生物樣品中物種分析工具最佳選擇之一。
第一部分研究是以液相層析結合感應耦合電漿質譜儀對水樣、樹葉樣品中Tl(I)及Tl(III)進行物種分析，並觀察樹葉樣品與同區域土壤樣品中鉈含量的分布關係。層析系統中，利用離子對逆相層析機制將 Tl(I)、Tl(III)分離，使用C-8管柱，並以Tetra-n-butylammonium phosphate（TBAP）做為離子對試劑，Diethylenetriamine-pentaacetic acid（DTPA）為螯合試劑。分離條件最適化探討後，可於3分鐘內將Tl兩物種快速分離，且偵測極限皆低至3 pg mL-1。以此開發之系統對水樣SRM進行分析，與標準參考值相當吻合；並分析中山大學旁表面水、美術館湖水，其回收率介於96-102%間，證明此系統的可行性。樹葉樣品則選擇釋迦葉為萃取對象，利用超音波振盪三十分鐘的方式，此方式為一簡便、快速之萃取方法，且萃取效率可達99%以上。實驗結果顯示存在樹葉樣品中的皆是較穩定但毒性較高的 Tl(I)。另外也觀察到同區域取得的樹葉與土壤中之鉈含量彼此具有正相關性。
第二部分則以離子層析結合感應耦合電漿質譜儀對食用油中砷物種的分析。使用陰離子交換管柱，以梯度沖提的方式同時分離六個砷物種，包含Arsenite(As(III))、Arsenate(As(V))、Monomethylarsonic acid(MMA)、Dimethylarsinic acid(DMA)、Arsenobetaine(AsB)及Arsenocholine(AsC)，其偵測極限分別為0.024、0.013、0.010、0.008、0.009、0.010 ng mL-1，r2均為0.9995以上，訊號面積RSD除了As(III)較高之外，其餘皆在3.5%以下（n = 5）。分離條件最適化後，六種砷物種可於7分鐘內完成分離。在實驗中，食用油樣品之總量測定不同於傳統微波消化方式，本實驗是利用乳化法（Emulsion）直接進樣，不僅降低前處理的複雜性，更減少了消化過程中可能輸入的污染。食用油萃取方法則是以0.5% (v/v) HNO3配置於80% (v/v) MeOH之溶液作為萃取試劑，以微波萃取（80℃）2小時後，以減壓濃縮機（Rotary Evaporator）於70℃水浴下，將部分甲醇揮發掉。食用油樣品萃取前添加適量濃度之六個砷物種標準品，並於萃取後，以HPLC-ICP-MS定量，物種回收率在93-105%間，表示此萃取方法的可行性。實驗中，並取得三種來自不同店家使用過的炸油進行物種分析，且比較使用前及使用後的砷含量。實驗結果顯示使用前後之食用油樣品其砷含量有所不同，且不同來源的食用油樣品其砷物種的分布也不同。

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摘要......................I
謝誌.....................IV
目錄.....................V
圖目錄.....................VIII
表目錄.....................X

第一章 離子對逆相層析法結合感應耦合電漿質譜儀於環境樣品中鉈物種分析之應用
壹、前言.....................1
貳、實驗部分.....................4
一、儀器裝置.....................4
二、試劑藥品和溶液的配製.....................5
參、實驗過程.....................9
一. 液相層析分離條件最適化.....................9
二. 校正曲線、偵測極限的估計.....................11
三. 再現性.....................11
四. 環境樣品分析.....................11
肆、結果與討論.....................16
一、液相層析條件最適化探討.....................16
二、再現性.....................27
三、校正曲線與偵測極限的估計.....................27
四、環境樣品分析.....................32
伍、結論.....................45
陸、參考文獻.....................46
第二章 離子層析法結合感應耦合電漿質譜儀於食用油中
砷物種分析之應用
壹、前言.....................46
貳、實驗部分.....................49
一、儀器裝置.....................49
二、試劑藥品和溶液的配製.....................50
參、實驗過程.....................52
一. 液相層析分離條件最適化.....................52
二. 校正曲線、偵測極限的估計.....................53
三. 再現性.....................53
四、食用油樣品分析.....................56
肆、結果與討論.....................60
一、液相層析條件最適化探討.....................60
二、再現性.....................71
三、校正曲線與偵測極限的估計.....................71
四、萃取條件最適化.....................75
五、食用油樣品分析.....................79
伍、結論.....................91
陸、參考文獻 ......................................... 92

第一章
圖1-1 HPLC-ICP-MS系統圖.....................6
圖1-2 TBAP及DTPA之結構式.....................8
圖1-3 離子對作用機制示意圖.....................10
圖1-4 植物樹葉樣品萃取流程圖.....................13
圖1-5 物種分析實驗流程圖.....................15
圖1-6 TBAP濃度對層析分離的影響.....................17
圖1-7 DTPA濃度對層析分離的影響.....................19
圖1-8 動相pH值對層析分離的影響.....................20
圖1-9 動相pH值對分析物滯留時間關係圖.....................21
圖1-10 動相中甲醇濃度對層析分離的影響.....................23
圖1-11 動相流速對層析分離的影響.....................25
圖1-12 水樣標準參考樣品之層析圖.....................33
圖1-13 中山大學旁滲出水之層析圖.....................36
圖1-14 美術館湖水之層析圖.....................37
圖1-15 中山大學旁水泥廠釋迦葉之層析圖.....................40
圖1-16 台東市區釋迦葉之層析圖.....................41
第二章
圖2-1 砷物種於各pH值環境下之化學式及pKa值.....................57
圖2-2 各物種之結構式.....................58
圖2-3 食用油乳化液樣品製備流程圖.....................61
圖2-4 食用油樣品萃取流程圖.....................63
圖2-5 改變動相pH值對層析分離的影響.....................65
圖2-6 動相pH值對分析物滯留時間之關係圖.....................66
圖2-7 改變動相A之碳酸銨濃度對層析分離的影響..............68
圖2-8 改變動相甲醇濃度對層析分離的影響.....................70
圖2-9 改變動相切換時間對層析分離的影響.....................73
圖2-10 改變動相ramp時間對層析分離的影響.....................74
圖2-11 不同萃取試劑於食用油中砷萃取量之相對訊號...........82
圖2-12 不同萃取時間於食用油中砷萃取量之相對訊號............83
圖2-13 不同萃取溫度於食用油中砷萃取量之相對訊號............85
圖2-14 萃取試劑為0.5% (v/v) HNO3配置於80% (v/v) MeOH中，維持不同萃取時間對於油中砷萃取量之相對訊號.....................93
圖2-15 Oil#1萃取後所得砷物種之層析圖.....................94
圖2-16 Oil#2萃取後所得砷物種之層析圖.....................95
圖2-17 Oil#3萃取後所得砷物種之層析圖.....................96
第一章
表1-1 動相流速對分析物訊號之影響 .....................26
表1-2 LC-ICP-MS 系統操作條件.....................28
表1-3 鉈物種的滯留時間及分析訊號之再現性.....................29
表1-4 鉈物種之校正曲線及偵測極限..................... 30
表1-5 偵測極限之比較.....................31
表1-6 以LC-ICP-MS測定SRM水樣中鉈物種含量.....................34
表1-7 以LC-ICP-MS測定水樣中鉈物種含量.....................38
表1-8 以LC-ICP-MS測定釋迦葉中鉈物種含量.....................42
表1-9 同一區域樹葉及土壤樣品鉈總量比較.....................44
第二章
表2-1 動相A碳酸銨濃度對分析物訊號之影響.....................69
表2-2 動相中甲醇濃度對分析物訊號之影響.....................72
表2-3 LC-ICP-MS系統操作條件.....................76
表2-4 六種砷物種的滯留時間及分析訊號之再現性.................78
表2-5 以LC-ICP-MS測定砷物種之校正曲線及偵測極限..........79
表2-6 以LC-ICP-MS測定砷物種之偵測極限比較.....................80
表2-7 以乳化方式對油品中的As定總量.....................87
表2-8 食用油樣品砷物種萃取量與總量之比較.....................88
表2-9 萃取後殘餘的油樣品砷含量與總量比較.....................89
表2-10 食用油樣品砷物種萃取量與總量之比較.....................92
表2-11 以LC-ICP-MS測定油中砷物種之含量.....................98

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