第一部份研究利用逆相層析法結合動態反應槽感應耦合電漿質譜儀對食米中鉻物種進行分析。使用C18逆相層析管柱，以0.5 mmol L-1 TBAP、0.1 mmol L-1 EDTA以及2% (v/v)甲醇(pH 6.9)作為動相，以等位沖堤方式在6分鐘內分離Cr(III)和Cr(VI)。為了得到較好的偵測極限，以超音波霧化器作為霧化輸入裝置，除了提升霧化效率，還能利用加熱與冷凝系統去除動相中的水及有機溶劑，利於提升分析物訊號並降低背景訊號。此外，亦藉由動態反應槽搭配NH3作為反應氣體，減少偵測52Cr及53Cr時來自40Ar12C+、40Ar13C+等多原子離子光譜干擾。Cr(III)與Cr(VI)之偵測極限分別為0.011 ng mL-1及0.012 ng mL-1，而滯留時間、波峰高度、波峰面積之再現性RSD皆小於3%。樣品於動相中添加1% (v/v) HF及2 mmol L-1 EDTA作為萃取試劑，以微波輔助方式萃取，並利用標準參考樣品NIST SRM 1573a Tomato Leaves驗證方法準確性。最後將此方法用於食用白米及米精樣品中鉻物種之分析。
第二部份利用陰離子交換層析法結合動態反應槽感應耦合電漿質譜儀對食米中進行Cr(VI)分析。使用PRP-X100作為管柱，以 80 mmol L-1 NH4NO3及1% (v/v)甲醇(pH 8.8)作為動相，可於6分鐘內分離Cr(III)和Cr(VI)。搭配NH3作為反應氣體，降低使用ICP-MS偵測52Cr及53Cr 所產生之光譜干擾。Cr(VI)之偵測極限為0.064 ng mL-1，而滯留時間、波峰高度、波峰面積之再現性RSD皆小於2.9%。樣品於動相中添加5% (v/v)四甲基氫氧化銨(TMAH)作為萃取試劑，使用超音波震盪輔助方式萃取。將此方法應用於標準參考樣品NIST SRM 1573a Tomato Leaves、食用白米、米精及糙米樣品中Cr(VI)之分析。最後將兩部份研究之方法所測得標準參考樣品NIST SRM 1573a Tomato Leaves、食用白米以及米精中Cr(VI)含量結果進行t-test分析，結果顯示於95%信賴區間內不具明顯差異，證實兩部份之分析方法皆具準確性。

First part of research focused on reversed-phase chromatography with dynamic reaction cell ICP-MS for determination of chromium species in variety of rice samples. The separation was performed on reverse-phase column C18 using isocratic elution program which contain 0.5 mmol L-1 TBAP, 0.1 mmol L-1 EDTA and 2% (v/v) methanol at pH 6.9. To further species separation of Cr(III) and Cr(VI) was achieved within 6 mins. The ultrasonic nebulizers (USN) were utilized as atomized input device to further achieve better detection limit. USN can improve enormously atomization efficiency. In addition, the desolvation and condensation system of USN can remove most of the unwanted water and organic solvents in mobile phase which implies that decline the background. To further achievement, the potentially interfering 40Ar12C+ and 40Ar13C+ at the chromium mass m/z 52 and m/z 53 were reduced by dynamic reaction cell using NH3 as a reaction gas were applied. The detection limits of Cr(III) and Cr(VI) were obtained 0.011 and 0.012 ng mL-1, respectively. Besides, relative standard deviations of retention time, peak height, peak area was achieved less than 3%. Moreover, sample were extracted using microwave heating with 1% (v/v) HF and 2 mmol L-1 EDTA in mobile phase, along with this proposed method was applied and then validated by standard reference samples by NIST SRM 1573a Tomato Leaves, in real world application this proposed method were further applied to several samples (white rice and also rice cereals).
In second part of research focused on anion-exchange chromatography with dynamic reaction cell ICP-MS for determination of Cr(VI) species in rice samples. The separation of Cr(III) and Cr(VI) was performed by using PRP-X100 column with 80 mmol L-1 NH4NO3 and 1% (v/v) methanol at pH 8.8. The overall separation time this can be carried out within 6 mins accompanied by spectral interference in ICP-MS at chromium m/z 52 and m/z 53 were reduced using NH3 as a reaction gas. The detection limits of Cr(VI) were obtained 0.064 ng mL-1. In addition, relative standard deviations of the retention time, peak height, and peak area are all less than 2.9%. Besides, the samples were extracted with 5% (v/v) TMAH in mobile phase by ultrasonic extraction method. Based on that, proposed this method was applied to standard reference sample NIST SRM 1573a Tomato Leaves, with several rice samples (white rice, rice cereal, and brown rice). In conclusion, the t-test were also utilized to determine the Cr(VI) species of this proposed research which implies that both methods were performed on standard reference sample NIST SRM 1573a Tomato Leaves, and multiple rice samples. The results were shown that there was no significant difference in the proposed two methods with successfully achieved 95% confidence level.

目 錄
論文審定書 i
誌謝 ii
摘要 iii
Abstract iv
目錄 vi
圖目錄 … viii
表目錄 … x


第一章 逆相層析法結合動態反應槽感應耦合電漿質譜儀於食用白米及米精中鉻物種分析之應用
壹、前言 1
貳、實驗部份 5
一、儀器裝置 5
二、試藥及溶液之配製 8
三、樣品及標準參考樣品 9
參、實驗流程 10
一、液相層析分離條件最適化 10
二、超音波霧化器系統最適化 10
三、DRC-ICP-MS系統最適化 10
四、再現性 11
五、校正曲線與偵測極限 12
六、萃取條件最適化 12
七、真實樣品分析 12
肆、結果與討論 17
一、液相層析條件之最適化探討 17
二、超音波霧化器系統最適化探討 20
三、DRC-ICP-MS系統最適化條件 25
四、再現性 36
五、校正曲線與偵測極限的估計 36
六、萃取最適化條件 40
七、方法準確性的評估 41
八、真實樣品分析 49
伍、結論 57
陸、參考文獻 58


第二章 陰離子交換層析法結合動態反應槽感應耦合電漿質譜儀於食用白米、米精及糙米中Cr(VI)分析之應用
壹、前言 63
貳、實驗部份 65
一、儀器裝置 65
二、試藥及溶液之配製 67
三、樣品及標準參考樣品 68
參、實驗流程 68
一、液相層析分離條件最適化 68
二、DRC-ICP-MS系統最適化 69
三、再現性 69
四、校正曲線與偵測極限 69
五、萃取條件最適化 70
六、真實樣品分析 70
肆、結果與討論 74
一、液相層析條件之最適化探討 74
二、DRC-ICP-MS系統最適化條件 77
三、再現性 83
四、校正曲線與偵測極限的估計 90
五、萃取最適化條件 90
六、真實樣品分析 95
伍、 結論 110
陸、 參考文獻 111

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第二章 陰離子交換層析法結合動態反應槽感應耦合電漿質譜儀於食用白米、米精及糙米中Cr(VI)分析之應用
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