Abstract
本研究發展層析與光譜及質譜之連線技術,並應用於環境及生物樣品中微量元素及其物種之分析.為期有效地達成可靠,靈敏及快速之分析目標,研究中建立線上管柱分離方法,並以其與氫化產生原子吸收光譜儀及感應耦合電漿質譜儀連線,進行樣品的分析.除了分析方法的開發外,本研究特別針對多種元素進行物種分析及基質分離機構進行探討.本論文分為三個主要部份,其一為發展一複合式氣液分離裝置,除了用以評估分離膜之效率外,並將其與層析系統及氫化產生原子吸收光譜儀進行連線,以應用於地下水中之砷物種分析.第二部份則為發展陰離子交換管柱與感應耦合電漿質譜儀的連線系統,並應用於生物及環境樣品中之鍺,砷及硒元素之濃度測定.研究中發現以所建立之連線系統,可將樣品基質所導致之質譜性干擾(利如35Cl37Cl對72Ge,及40Ar35Cl對75As),有效的予以分離;本方法之偵測極限,對各元素均可低達sub-ppb之程度.本論文之最後一部份,係發展高效率形體篩分層析法與感應耦合電漿質譜儀之連線技術,並應用於人類體液中砷及硒蛋白質之分子量的分佈研究.研究中同時探討小分子物種在形體篩分層析管柱分離時之可能機構,另並以所建立的連線技術應用於烏腳病病患及對照組之體液進行分析.The present study is aimed to develop hyphenated techniques ofchromatography with spectrometric detection for determinationof trace elements (As, Se and Ge) and their speciesdistribution in environmental and biological samples. In orderto achieve reliable, sensitive and rapid analytical purpose,the hyphenated techniques based on on-line separation followedby detection with hydride-generation atomic absorptionspectrometry (HGAAS) and inductively coupled plasma massspectrometry (ICP-MS) are employed. There are three main partsconsisted in this work. Firstly, a combined gas-liquidseparator was established for the evaluation of membraneefficiency, and then applied for the determination of arsenicspecies in groundwaters by coupled with liquid chromatographyand HGAAS. In a subsequent part, a method was developed for thedetermination of germanium, arsenic and selenium in themicrowave digested urine and blood samples by an on-line anion-exchange separation process followed by ICP-MS measurement.With this on-line analytical system, the determination of 72Geand 75As could be completely free from the interference causedby 35Cl37Cl and 40Ar35Cl, and the detection limits obtained forGe, As and Se could be as low as sub-ppb levels. And finally,the high performance size exclusion chromatography (HPSEC)followed by detection with UV and ICP-MS were developed for thedetermination of size distribution of As and Se in the bloodsamples. The patterns of arseno- and seleno-proteins obtainedby the proposed system were discussed.