Abstract
為進行生物樣品中微量元素及其物種的準確分析，本論文利用感應耦合電 漿質譜儀，並配合發展多套分析技術，以提供準確、快速的分析能力。本 論文共分為三部份，第一部份是發展自動化樣品前處理系統並配合感應耦 合電漿質譜儀，以進行血液樣品中微量及超微量元素的分析。血液樣品在 自動化樣品前處理系統中先經線上微波消化，再以線上前濃縮系統進行待 測元素的濃縮及干擾基質的分離，最後再以高靈敏的感應耦合電漿質譜儀 進行測定。整個工作在自行設計的程式及自行組裝的自動控制電路控制之 下，每小時可完成 6 個樣品中 Fe、Ni、Cu、Zn 及 Pb 元素的準確分析 。在第二部份中，我們發展三種不同的層析與元素選擇性偵測儀器（原子 吸收光譜儀及感應耦合電漿質譜儀）的連線分析系統，以進行烏腳病流行 地區居民尿液中砷元素之物種分析研究。在所建立的陰離子層析與元素選 擇性偵測儀器的連線系統中，我們可在 15 分鐘內完成四個主要毒性的砷 物種的分析與鑑定，包括三價砷、五價砷、單甲基砷與二甲基砷，除此以 外，我們在居民的尿液中亦發現了其它三種未知的砷物種。此系統並實際 完成了 47 個皮膚癌病患與 255 個健康居民的尿液樣品分析，以進行該 地區居民體內砷甲基化能力與癌症罹患率之間的關係。在第三部份，本論 文發展同位素稀釋法配合感應耦合電漿質譜儀，以進行血液樣品中微量鉛 元素的高精密與高準確分析。本技術並用以評估在國內自行利用豬血作為 標準參考血液樣品的可行性。 The aim of this study is to develop different analytical systems for the accurate determination of trace and ultra-trace elements in biological materials by ICP-MS. Three major parts are included in this study. Firstly, an fully automated sample pretreatment system on-line coupling microwave digestion, preconcentration/ separation and ICP-MS measurement is developed for the determination of trace metals (Ni, Cu, Fe, Zn and Pb) in blood and serum samples. The results indicate that the system p. □des with an expert control system can automatically execute sample uptake, microwave digestion, pH adjustment, matrix separation, preconcentration, measurement, calibration and data processing with the sample throughput of 6 samples/hr. Secondly, various hyphenated analytical systems consisting of HPLC, hydride generation (HG), and atomic absorption spectrometry (AAS) or ICP-MS are developed and applied to arsenic speciation in the urine samples of residents from the blackfoot disease endemic areas. With the established anion- HPLC system, chloride interference on the determination of arsenic by ICP-MS can be completely eliminated, and four major toxic arsenic species (AsIII, AsV, DMA and MMA) can be separated in 15 minutes. A total of seven arsenic species are found in the urine samples, they include arsenite, arsenate, monomethylarsonic acid, dimethylarsinic acid and three unknown species. Finally, HPLC-HG-AAS system has been applied to the determination of arsenic species in the urine sample of 47 cancer cases and 255 healthy controls. The results obtained are to be used for correlation study between arsenic speciation and the capability of methylation in urine sample of residents from the BFD endemic areas. The third part of this work is aimed to develop an ID-ICP-MS system for accurate and precise determination of lead in blood samples and to explore the feasibility by using this technique to certify lead concentration in porcine blood to be used as a candidate SRM. The results indicate that under optimized operation parameters, the good precision and accuracy for the determination of lead concentration in blood can be obtained.