臺灣博碩士論文加值系統

傳統中藥大致可分為植物性、動物性及礦物性等三大類，本研究取自市售坊間常用種礦物性中藥硼砂、龍骨粉、牡蠣粉、鑪乾石、禹余糧等，以傳統強酸氧化迴流加熱消化法，用硝酸消化分解破壞樣品中有機物質的成分，防止光譜干擾(spectral interferences)及有機殘留物會堆積在燃燒頭(burner head )與噴灑室(spray chamer)。最後利用火燄式原子吸收光譜儀(flame atomic absorption spectrometry FAAS)，檢測其中微量重金屬鉛(lead)、鎘(cadmium)、銅(copper)及鎳(nickel)的含量。
研究中對分析方法的準確度(accuracy)、精密度(precision)、 偵測極限LOD(limit of detection)、檢出限量LOQ(limit of quantitation)、線性(linearity )與線性相關係數( R：linear correlation coefficient )及回收率(recovery )進行評估，以建立分析方法並確效。儀器方法的校正以校正曲線法(calibration curve method)及標準添加法(standard addition method)兩者加以比較，尋求其最適切性，以確認基質干擾的效應對實驗結果的影響。
本研究所獲得主要的結論為：(1) 在鉛、鎘、銅及鎳等四種金屬元素的回收率方面，校正曲線法及標準添加法兩者加以比較。以整體回收率平均值來看，不論在哪一種重金屬檢測中，標準添加法的回收率表現皆比校正曲線法佳。表示標準添加法比校正曲線法的準確性較高，而且測量值較近於實際值(2) 在精密度CV﹪方面，都能控制在 4﹪以下，表示實驗的分析方法，已經能合乎品質控制的標準(3) 受基質效應的影響明顯時，在標準添加法中測值比校正曲線法偏高，因為校正曲線法忽略了真實溶液的基質效應。除了使用校正曲線法來定量外，可以再採用標準添加法來分析，所得的結果可靠性較高，表示當有基質存在時，我們可使用標準添加法來分析加以改善(4) Pb、Cd、Cu及Ni 的測定中，在鑪乾石檢品，使用校正曲線法及標準添加法含鉛量分別為795.00 μg/g及812.50 μg/g；在龍骨粉檢品中，含鎘量分別為15.00 μg/g及15.00 μg/g，含鎳量分別為28.13 μg/g及28.75 μg/g。

There are three kinds of traditional Chinese medicine including plants, animals, and minerals . The samples of this work used are ordinary, marketable, and mineral Chinese medicine-- borax, dragon teeth, oyster, smithsonite, limonitium. In addition, we use traditional digest method (concentrated acid oxidation) to digest the organic substances in samples. This method could avoid that spectral interferences would occur in collecting experimental data and that organic substance accumulated on the burner head and spray chamber. The final, We use flame atomic absorption spectrometry (FAAS) to trace the amounts of lead, cadmium, copper, and nickel.
In the research, we evaluate the accuracy, precision, limit of detection, limit of quantitation, linearity, linear correlation coefficient, and recovery for the analytical method to establish a good and accurate analytical model. With comparison between calibration curve method and standard addition method, the calibration of instrumental method could be acquired and confirm the affects of matrix interference in experimental results.
The main conclusions in the work are (1) In the aspect of Pb, Cd, Cu, and Ni recoveries, the standard addition method is better than calibration curve method with average of the whole recovery for any above -mentioned elements. The standard addition method owns higher accuracy than the calibration curve method and Its measured values are near the real values. (2) In the aspect of precision, the all of measured values are controlled under CV 4%, it indicts us that the analytical method had considered with standard quality control. (3) The measured values of standard addition method are higher than calibration curve method, which ignores the matrix effect in real solution. We also used standard addition method to confirm the results besides using calibration curve method to quantify for sample. Therefore, the results are more reliable. The standard addition method might improve the analytical method when there is matrix in samples. (4) This analysis detected Pb, Cd, Cu, and Ni in Smithsonite with concerntrations of 795.00 μg/g and 812.50 μg/g for Pb , in Dragon Teeth with concerntrations of 15.00 μg/g and 15.00 μg/g for Cd and 28.13 μg/g and 28.75 μg/g for Ni individually by using the calibration curve method and the standard addition method.

第一章 導論 頁次

第一節 前言…………………………………………………………..1

第二節 前人研究……………………………………………………..2

第三節 中藥中有害重金屬元素Pb、Cr、Cu及Ni的探討……....…..3
1-3-1微量重金屬添加在中藥中的背景探討……………..…….3
1-3-2中藥中有害重金屬Pb、Cd、Cu及Ni的污染來源…….4


第四節 原子吸收光譜儀( atomic absorption spectrometry AAS)的簡介…………………………………………………...…..10
1-4-1 原子吸收光譜儀的基本原理………………..…….……10
1-4-2 原子吸收光譜儀在重金屬分析的應用原理…………...12
1-4-3 原子吸收光譜儀的儀器構造………….………………..13

第二章 實驗方法部份…………………………………………………15

第一節 儀器與設備…………….....………………………………15

第二節 Pb、Cd、Cu及Ni元素在原子吸收光譜儀的檢測分析條件………………………………………………………….15

第三節 實驗器皿之清洗……………………………….….……….16

第四節 實驗藥品……………………………………….…………..17
2-4-1 試藥…………………………………………….……….17
2-4-2 中藥樣品……………………………………….……….17
2-4-3 中藥樣品的前處理…………………….……………….19


第五節 溶液的配製…………………………………….………….21
2-5-1 試藥溶液的配製………………………………….…….21
2-5-2 標準溶液的配製………………………….…………….21
2-5-3 檢品溶液的配製……………………….……………….22

第六節 分析方法的建立…………………………………….…..23
2-6-1 準確度(accuracy)………………………………...……...23
2-6-2 精密度(precision)……………………………….………23
2-6-3 偵測極限 (limit of detection：LOD)與檢出限量(limit of quantitation：LOQ)………………………….………..23
2-6-4 線性(linearity )與線性相關係數( R：linear correlation coefficient )………...…………….……….……………24
2-6-5 中藥中重金屬鉛、鎘、銅及鎳含量的測定..…….….…24

第七節 樣品溶液分析方法的選擇………………………………25
2-7-1 校正曲線法( calibration curve method )……………....25
2-7-2 標準添加法(standard addition method )….…..……… 25

第八節 中藥檢液中鉛、鎘、銅及鎳含量的測定……………....27
2-8-1 校正曲線法…………………….…………………..…..27
2-8-2 標準添加法………………………………………...…..27

第三章 結果與討論…………………………………….……………...28

第一節 分析方法的確效試驗……………………………………28
3-1-1 線性與線性相關係數R……………..……..….…….…28
3-1-2 準確度………..……………………..………….……….32
3-1-3 精密度…………………………………………….…….37
3-1-4 儀器的偵測極限(LOD)與檢出限量(LOQ)……………42

第二節 中藥中鉛、鎘、銅及鎳含量的測定………………….….44
3-2-1 校正曲線法………………………...……..…………….44
3-2-2 標準添加法………...…………….....………….……….46

第四章 結論………………………………….………….….………….67

第五章 建議與展望……………………………………………………69
參考文獻………………………………………………….……….……70
附錄……………………………………………………………………..76

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