Explorations of electrothermal vaporization inductively coupled plasma time-of-flight mass spectrometry for isotopic analysis
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The application of inductively coupled plasma time-of-flight mass spectrometers (ICP-TOFMS) coupled to electrothermal vaporization (ETV) presents several unique analytical opportunities for isotopic analysis. This dissertation explores several subjects that utilize these characteristics in specific analytical applications. The viability of using the thermal programming abilities of the ETV in order to separate Rb and Sr is explored. These elements are isobaric at m/z 87, and must normally be separated prior to analysis for isotopic studies. Their disparate thermal properties allow them to be separated in time by the ETV allowing for simpler, faster isotope ratio analysis with less opportunity for contamination. A test case using standard potassium feldspar is found to produce moderately accurate and precise results. TOF instruments are of interest for isotope ratio analysis due to inherent isotope ratio precision. However, it has been observed that when operated in the analog data collection mode the isotope ratios observed possess a previously uncharacterized inaccuracy. This bias is rooted in variable detection efficiency of arriving ions, which can be corrected for with an algorithm described within. A method of determining the effective detector efficiency as a function of signal is presented, as well as an evaluation of the effectiveness of ratio correction. The use of ETV with TOF for isotope dilution analysis is explored. Correction of transient signals for efficiency effects is discussed, as well as the viability of using the autosampler for mixing of the solution and spike. A final study presents explores the combination of the ETV and TOF for analysis of a large number of elements from a brief transient signal. A library of peptide covered beads is analyzed for binding capacity to a variety of metals. Solutions containing metals stripped from the beads are analyzed to determine the binding capacity and specificity of the peptide sequence. The beads themselves are also analyzed for metal content using the ETV as an indicator of the efficiency of metal stripping off of the beads.