化學蒸氣生成（Chemical Vapor Generation，CVG）是一種廣泛應用在原子光譜及質譜分析上的進樣方式，此方法利用氣體生成技術將分析物與溶液中之基質分離，具有增加分析物傳輸效率、提升靈敏度、降低偵測極限及減輕特定光譜干擾等優點。本研究結合CVG與感應耦合電漿質譜儀（Inductively coupled plasma mass spectrometry，ICP-MS）偵測土壤及中草藥樣品中重金屬元素。
　　研究分為兩個部分，第一部分利用流動注入化學蒸氣生成技術結合動態反應室感應耦合電漿質譜儀（FI-CVG-DRC-ICP-MS）分析土壤樣品中銅、鋅及鎘的含量。ICP-MS以傳統氣動式霧化器進行土壤中銅、鋅及鎘分析時，因樣品中含有高濃度的鈦、鉬基質，其生成之TiO+及MoO+多原子離子會造成同質量干擾而影響銅、鋅及鎘之分析結果。藉由動態反應室（Dynamic Reaction Cell，DRC）降低光譜干擾時，無法以單一反應氣體同時克服TiO+及MoO+的干擾，故本研究期望藉由CVG加上氣液分離裝置將分析物與樣品溶液中之基質分離，以減輕TiO+及MoO+干擾。本研究探討了蒸氣生成系統的最適化條件，包括載體溶液中8-hydroxyquinoline、Co(II)與HNO3含量、NaBH4濃度、混合線圈長度及反應試劑流速等對分析物訊號的影響。在最適化條件下，顯示以CVG做為進樣裝置能有效將Mo分離，同時降低了Ti 對分析物離子訊號的干擾。而為了達到定量的準確性，進一步使用 DRC系統來改善TiO+的光譜干擾，研究中以NH3作為反應氣體，探討 DRC系統之最適化條件。將本研究所建立之FI-CVG-DRC-ICP-MS對土壤標準參考樣品Montana Soil及San Joaquin Soil進行分析，其結果與標準參考值相吻合，證明了使用本系統對土壤中銅、鋅及鎘元素同時進行偵測的可行性。
　　第二部分則利用泥漿進樣結合CVG-ICP-MS測定中草藥樣品中砷、汞及鉛元素的含量。泥漿進樣具有簡化樣品前處理程序與減少污染物導入等優點，實驗中以中草藥藥粉為基質，探討CVG-ICP-MS系統條件之最適化，包括樣品及載體溶液中HCl與Citric acid濃度、NaBH4濃度K3Fe(CN)6濃度等。在最適化條件下於樣品基質中添加 0.5 ng mL-1砷與汞的元素標準溶液以測定訊號再現性，所測得之分析物訊號波峰面積相對標準偏差（RSD）皆於3.3%以下（n = 5）。由於樣品基質的差異造成了標準添加法及水溶液校正曲線法靈敏度的不同，因此本研究以標準添加法及同位素稀釋法進行定量。所得砷、汞及鉛的偵測極限皆小於10 pg mL-1。最後，將所開發之方法應用於標準參考樣品 NIST SRM 1547 Peach leaves及 NIST SRM 1573a Tomato leaves的分析，且檢測三種市售中草藥藥粉中砷、汞及鉛的含量，並將其結果與傳統微波消化定量作比較，進一步驗證此分析方法之準確性與可行性。

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目 錄
論文提要 I
謝誌 IV
目錄 V
圖表目錄 IX

第一章 流動注入化學蒸氣生成技術結合感應耦合電漿質譜儀於土壤樣品中銅、鋅及鎘之分析應用
壹、 前言 1
一、 研究背景 1
二、 流動注入分析法（Flow injection analysis，FIA） 5
三、 化學蒸氣生成法（Chemical vapor generation，CVG） 6
四、 動態反應室系統（Dynamic reaction cell，DRC） 11
五、 同位素稀釋法（Isotope dilution，ID） 13
貳、 實驗部份 15
一、 儀器裝置 15
二、 試劑藥品和溶液的配製 18
參、 實驗過程 21
一、 化學蒸氣生成系統各參數之探討 21
二、 ICP系統操作條件之探討 25
三、 光譜（同質量）干擾 26
四、 DRC系統之最適化 27
五、 再現性 28
六、 校正曲線與偵測極限的估計 28
七、 樣品前處理及分析 29
肆、 結果與討論 31
一、 化學蒸氣生成系統各參數之探討 32
二、 ICP系統操作條件之探討 43
三、 光譜（同質量）干擾 46
四、 DRC系統之最適化 52
五、 再現性 60
六、 校正曲線與偵測極限的估計 60
七、 樣品前處理及分析 64
伍、 結論 69
陸、 參考文獻 70




第二章 流動注入化學蒸氣生成技術結合感應耦合電漿質譜儀於泥漿中草藥樣品中砷、汞及鉛之分析應用
壹、 前言 76
一、 研究背景 76
二、 金屬的毒性及對人體的危害 79
貳、 實驗部份 80
一、 儀器裝置 81
二、 試劑藥品和溶液的配製 83
參、 實驗過程 85
一、 化學蒸氣生成系統各參數之探討 85
二、 ICP系統操作條件之探討 89
三、 光譜（同質量）干擾 91
四、 再現性 91
五、 校正曲線與偵測極限的估計 91
六、 樣品前處理及分析 92
肆、 結果與討論 95
一、 化學蒸氣生成系統各參數之探討 95
二、 ICP系統操作條件之探討 106
三、 光譜（同質量）干擾 109
四、 再現性 112
五、 校正曲線與偵測極限的估計 112
六、 樣品前處理及分析 119
伍、 結論 127
陸、 參考文獻 128



圖表目錄
第一章

圖1-1 photo-CVG系統示意圖 10
圖1-2 DRC-ICP-MS 儀器示意圖 12
圖1-3 流動注入化學蒸氣生成系統裝置圖 17
圖1-4 樣品及載體溶液中8-hydroxyquinoline濃度對訊號之影響 35
圖1-5 樣品及載體溶液中Co(II)濃度對分析物訊號之影響 37
圖1-6 NaBH4濃度對分析物訊號之影響 38
圖1-7 載體溶液及樣品中所含HNO3濃度對分析物訊號之影響 39
圖1-8 混合捲管長度對對分析物訊號之影響 41
圖1-9 反應試劑流速對分析物訊號之影響 42
圖1-10 電漿功率對分析物訊號之影響 45
圖1-11 載送氣體流速對分析物訊號之影響 47
圖1-12 模擬基質干擾程度 48
圖1-13 反應氣體NH3流速對63Cu(NH3)2+分析物訊號之影響 53
圖1-14 反應氣體NH3流速對68Zn分析物訊號之影響 54
圖1-15 反應氣體NH3流速對111Cd分析物訊號之影響 55
圖1-16 改變Rpq值對63Cu(NH3)2+分析物訊號之影響 57
圖1-17 改變Rpq值對68Zn及111Cd 預估偵測極限值的影響 58
圖1-18 改變AFV對63Cu(NH3)2+、68Zn及111Cd分析物訊號的影響 59
圖1-19 NIST SRM 2711以FI-CVG-ICP-MS分析之訊號圖 68

表1-1 標準參考土壤樣品中鈦、銅、鋅、鉬及鎘之含量 4
表1-2 可形成氫化物元素的物理性質 7
表1-3 銅、鋅及鎘同位素之含量比 22
表1-4 不同錯合試劑對銅、鋅及鎘訊號之比較 33
表1-5 FI-CVG最適化條件 44
表1-6 分析物與干擾物訊號之關係 50
表1-7 多原子離子對Cu、Zn及Cd訊號及同位素比例測量的影響 51
表1-8 DRC-ICP-MS系統操作條件 61
表1-9 分析物訊號再現性 62
表1-10 標準添加法與校正曲線法之比較 63
表1-11 土壤樣品中銅、鋅及鎘之定量結果 66
表1-12 土壤樣品中銅、鋅及鎘之定量結果 67

第二章

圖2-1 流動注入化學蒸氣生成之系統裝置圖 82
圖2-2 中草藥泥漿樣品製備流程圖 93
圖2-3 樣品及載體溶液中Citric acid濃度對分析物訊號之影響 99
圖2-4 NaBH4濃度對分析物訊號之影響 101
圖2-5 樣品及載體溶液中HCl 濃度對分析物訊號之影響 102
圖2-6 K3Fe(CN)6 濃度對分析物訊號之影響 104
圖2-7 反應試劑流速對分析物訊號之影響 105
圖2-8 電漿功率對分析物訊號之影響 108
圖2-9 載送氣體流速對分析物訊號之影響 110
圖2-10 泥漿中藥樣品前處理步驟圖 120
圖2-11 SRM 1547以泥漿進樣FI-CVG-ICP-MS分析之訊號圖 123
圖2-12 SRM 1573a以泥漿進樣FI-CVG-ICP-MS分析之訊號圖 124

表2-1 國際間中藥材重金屬之限量標準 77
表2-2 鉛及汞之同位素含量比 86
表2-3 微波消化步驟設定條件 96
表2-4 不同有機酸對砷、汞及鉛訊號之比較 98
表2-5 不同長度之mixing coil對CVG訊號生成的影響 107
表2-6 FI-CVG-ICP-MS最適化條件 111
表2-7 STD mode及DRC mode訊號之比較 113
表2-8 分析訊號之再現性 114
表2-9 標準添加法與校正曲線法斜率之比較 115
表2-10 標準添加法偵測極限 117
表2-11 中藥材斜率之比較 118
表2-12 樣品中砷、汞及鉛之定量結果 122
表2-13 中藥樣品中砷、汞及鉛之定量結果 125
表2-13 中藥樣品中砷、汞及鉛之定量結果 126

第一章

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第二章

1. 盧芬鈴、陳儀驊、曾木全、羅吉方、林哲輝。2009。中藥材之重金屬檢驗(V)。藥物食品檢驗局調查研究年報，27: 51-64。

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4. Basgel, S.; Erdemoglu, S. B., Determination of mineral and trace elements in some medicinal herbs and their infusions consumed in Turkey. Sci. Total Environ. 2006, 359 (1-3), 82-89.

5. Liu, Z. F.; Sun, H. W.; Shen, S. G.; Li, L. Q.; Shi, H. M., Simultaneous determination of total arsenic and total selenium in Chinese medicinal herbs by hydride generation atomic fluorescence spectrometry in tartaric acid medium. Anal. Chim. Acta 2005, 550 (1-2), 151-155.

6. Deng, T.; Liao, M.; Jia, M., Arsenic speciation in Chinese herb Ligusticum chuanxiong hort by hydride generation atomic fluorescence spectrometry. Spectrosc. Lett. 2005, 38 (2), 109-119.

7. Long, Z.; Xin, J. J.; Hou, X. D., Determination of arsenic and mercury in Chinese medicinal herbs by atomic fluorescence spectrometry with closed-vessel microwave digestion. Spectrosc. Lett. 2004, 37 (3), 263-274.

8. Liu, D. L.; Ke, S. Y.; Ye, R.; Ding, M. Y., Determination of trace lead in traditional Chinese herbal medicine Astragalus by microwave digestion-CTAB enhancing-continual flow ingection hydride generation-ICP-AES. Spectrosc. Spectr. Anal. 2007, 27 (11), 2337-2340.

9. Shi, L. F.; Xue, D. F.; Xu, H. G.; Liu, H.; Teng, W. F., Determination of Pb, Cd, Hg and As in three sorts of Chinese traditional medicine treating tumor by ICP-MS. Spectrosc. Spectr. Anal. 2007, 27 (5), 1036-1037.

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