Electrospray Ionization – Mass Spectrometry (ESI-MS) has proven to be a valuable tool for monitoring metal-ligand complexants relevant to the nuclear fuel cycle. Analytical methods capable of near real-time accountability (NRTA) are necessary in order to achieve the material accountability goals of the International Atomic Energy Agency (IAEA). The soft nature of ESI enables the transfer of ligand, metal, and metal ligand complexes to the gas phase for detection by mass spectrometry. Identification of all species permits the detection of ligand degradation and provides a rapid technique for material accountability. Metal-ligand complexes relevant to the plutonium uranium refining extraction (PUREX) process were analyzed in both positive and negative ionization modes. In the following introduction, a brief description of the PUREX process is provided to establish the necessity of a new technique capable of NRTA. In addition, the fundamentals of micro – ESI, nano – ESI, and the fragmentation regions within the MS will be described in detail.
ESI-MS is routinely used qualitatively for determining the stoichiometry of metal-ligand complexes, but deviations from known solution speciation generated by the ESI-MS have prevented this technique from providing consistent and reliable quantitative data. Fundamental studies were performed to identify discrepancies between solution and gas phase speciation. Redox reactions and differing ionization efficiencies between the metal and complexant were primary factors causing alterations to solution speciation in the ESI source. Furthermore, the produced gas phase ions were altered by fragmentation regions within the MS. Establishing the fundamentals of metal-complexant speciation in ESI-MS will define the quantitative limits of this technique.
|Advisor:||Clark, Sue B.|
|Commitee:||Campbell, James A., Nash, Ken, Reilly, Peter|
|School:||Washington State University|
|School Location:||United States -- Washington|
|Source:||DAI-B 74/11(E), Dissertation Abstracts International|
|Subjects:||Analytical chemistry, Inorganic chemistry|
|Keywords:||Actinides, Complexation, Electrospray ionization, Lanthanides, Nuclear fuel cycle, Purex|
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